TOPICS I N INOI<(iANI(

A N D GENERAL, ( tII MIS I I < \

THE CHEMISTRY OF GOLD
A C O L L E C T I O N OF MONO(;llAl'llS 1, 1)l'I'l~1) 1iY

R. J , H. C L A K K

Department of C h e m i s t r y , Universit?, C'ollegc~L o r ~ d o ~2i 0. ( ; o r t l o t ~Slrc,c,l,

L o n d o n W C 1 H OAJ, England

MONOGRAPH l 6 RICHARD J . PUDDEPHATT

Sc~rliorLcclurcr,
I)cpczrln~cnlof Irtorgclnic, Physical ilnd Industriul Chcrnislry,
T h c University o f Liverpool.
O t h e r trlles m thc collectror~
C;roclc S t , P.O. B o x 147,
1 The Chemistry of Beryllium, by D A Everc,st ( o u t o f p r m t ) Lic~crpoolL 6 9 3 H X . Ergland
2 Inorganic Ion Exchangers, b5 (' B Amphlett ( o u t of print)
3 Introduction t o the Atomic Nucleus, by .l. G . Chninghame ( o u t of
print)
4 The Chemistry o f the Rare-Earth Elements, b y N. E. Topp (out of
print)
5 The Chemistry of Gallium, by I. A. Sheka, I. S. Chaus and T. T .
Mityureva ( o u t of print)
6 The Chemistry of Technetium and Rhenium, by R. D. Peacock ( o u t
of print)
7 The Chemistry of Selenium, Tellurium and Polonium, by K. W .
Bagnall ( o u t of print)
8 Interactions in Electrolyte Solutions, by G. H. Nancollas
9 Plasma Chemistry in Electrical Discharges, by F. K . McTaggart
1 0 The Chemistry of Niobium and Tantalum, by F. Fairhrother ( o u t
of print)
11 The Chemistry of Titanium and Vanadium, b y R. J. H. Clark
1 2 Active Carbon, by M. Smiiek and S. t e r n ? ( o u t of print)
1 3 The Chemistry of Uranium (Including Its Applications in Nuclear
Technology), by E. H. P. Cordfunke ( o u t of print)
1 4 The Chemistry of Thallium, by A. G. Lee (available from Applied
Science Publishers, Barking, England)
15 The Actinide Elements, by K. W. Bagnall ( o u t of print) ELSEVIER SCIENTIFIC PUBLISHING COMPANY
Amsterdam - Oxford - New York
(Volumes 1-15 were edited by P. L. Robinson) 1978
ELSEVIER SCIENTIFIC PUBLISHING COMPANY
3 3 5 Jan van Galenstraat
PREFACE
P.O. Box 211, Amsterdam, The Netherlands

Metallic gold has been most highly valued by man since the
Uzstributors for the United S t a t e s and Canada earliest times but, since the demise of the alchemists, the chem-
ical conlpounds of gold have not been studied as closely as
ELSEVIEH NORTH-HOLLAND INC
52, Vanderbilt Avenue those of other rare metals. This is perhaps partly due to the ease
New York, N Y. 10017 with which many gold compounds decompose hack to the
noble metal, but also due to the limited use of gold other than
as a monetary standard and for jewellery and other decorative
uses. Gold and its compounds have been regarded as the least
useful of the noble metals as catalysts, but recent progress
suggests that this situation may change significantly in the near
future. Applications of gold based on its physical and chemical
rather than its decorative properties account for a larger pro-
portion of the total gold used each year. For example, the use
of gold in micro-electronic circuits is increasing rapidly, and
thcre is increasing interest in the drtvelopment of new gold
complexes for LISV in the treatment of arthritis.
Along with this expanding use of gold, there has been an
impressive series of advances in the chemistry of gold com-
pounds. For many years, the chemistry was dominated by the
study of linear two-co-ordinate gold(1) complexes and square-
planar four-co-ordinate gold(lI1) complexes. Recently, however,
compounds of gold(1) and gold(II1) in which the metal has
higher co-ordination numbers have been studied and a new
I n c l u d e s bibliographical r e f erertces and Lndex . chemistry of gold(I1) and gold(V) has been developed. Advances
l. Gold. I. T i t l e . 11. S e r i e s .
~D181. ~9P8 ~~~~~~~~6 73-3627 have also been made in understanding the nature of compounds
ISBN o - i 4 l + - 4 1 6 2 : ~ - 2 with gold-metal bonds, and, in addition, exciting cluster com-
pounds of gold have been prepared and characterised. Organo-
O Elsevier Scientific Publishing Company, 1978
gold chemistry has seen many advances, ranging from the
All rights reserved. No part of this publication may be reproduced, synthesis of unstabilised alkylgold species like [AuMe,]- and
stored in a retrieval system or transmitted in any form or by any means, [AuMe,]; t o the preparation of carbene, alkene and alkyne
electronic, mechanical, photocopying, recording or otherwise, without complexes of gold. Many reactions are now better understood
t h e prior written permission of t h e publisher,
as a result of mechanistic studies, and structure determinations
Elsevier Scientific Publishing Company, P.O. Box 330, Amsterdam,
The Netherlands have been aided by the routine application of sophisticated
spectroscopic techniques.
Printed in The Netherlands Some of the aspects discussed above have been the subjects
 vii

of excellent review articles. but. at a time when gold chemistry

is undergoing an impressive renaissance. there is a clear need for
a monograph covering all aspects of gold chemistry . It is hoped
that this book will fill this gap and that it may stimulate
Preface . . . . . . . . . . . . . . . . . . . . v
further research. for there is still a great deal t o be learned about
gold and its compounds .
R . J . Puddephatt
Chapter 1. Introduction to the Chemistry of Gold
Occurrence of gold . . . . . . . . . . . . . . 1
Gold in sea water . . . . . . . . . . . . . . . 3
Recovery and purification of gold . . . . . . . . 4
Properties of the element . . . . . . . . . . . . 5
Colloidal gold . . . . . . . . . . . . . . . . 6
Isotopes of gold . . . . . . . . . . . . . . . 7
Chemical reactivity of gold . . . . . . . . . . . 9
Oxidation states of gold and the stereochemistries of
gold complexes . . . . . . . . . . . . . . 10
Ionisation energies and electron affinities of the Group
TB elements . . . . . . . . . . . . . . . . 14
Co-ordination number in gold(1) complexes . . . . 15
Oxidation-reduction potentials . . . . . . . . . 18
Stability of gold complexes . . . . . . . . . . . 22
Theoretical studies of bonding in gold complexes . . 24
The trans-effect and trans-influence . . . . . . . . 26
References . . . . . . . . . . . . . . . . . 28

Chapter 2 . Binary Compounds of Gold

Hydrides of gold . . . . . . . . . .
Halides of gold . . . . . . . . . . .
Pseudohalides of gold . . . . . . . .
Oxides and hydroxidks of gold . . . .
Sulphides. selenides and tellurides of gold
Gold(II1) fluorosulphate and nitrate . . .
Nitrides and other Group V derivatives .
References . . . . . . . . . . . .
Chapter 3 . G o l d ( I ) C o m p l e x e s
Carbonyl complexes . . . . . . . . . . . .
Isocyanide complexes . . . . . . . . . . . .
Cyanide complexes of gold(1) . . . . . . . . .
Nitrogen donor complexes . . . . . . . . . .
Phosphorus. arsenic and antimony donor complexes
Complexes with gold-oxygen bonds . . . . . .
Complexes with sulphur and selenium donor ligands
Halide complexes of gold(1) . . . . . . . . . .
References . . . . . . . . . . . . . . . .
Chapter 4 . G o l d ( I I ) Complexes
Dithiolate and related complexes of gold(I1) . . . . 70
Other stable gold(I1) complexes . . . . . . . . . 72
Gold(I1) complexes as reaction intermediates . . . . 74
References . . . . . . . . . . . . . . . . . 74
Chapter 5. G o l d f l l l ) Complexes
Complexes with carbon-donorligands . . . . . . . 76
Nitrogen-donor complexes of gold(II1) . . . . . . 77
Complexes with phosphorus. arsenic and antimony
donor ligands . . . . . . . . . . . . . . . 83
Nitratogold(II1) complexes . . . . . . . . . . . 85
Complexes with sulphur and selenium donor ligands . 85
Complex halides of gold(II1) . . . . . . . . . . 90
References . . . . . . . . . . . . . . . . . 93
Chapter 6 . G o l d ( V ) C o m p l e x e s
References . . . . . . . . . . . . . . . . . 97
Chapter 7 . Organogold C o m p l e x e s
U-Bondedorganogold(1) complexes . . . . . . . . 98
Reactions of organogold(1) complexes . . . . . . . 109
U-Bonded organogold(II1) complexes . . . . . . . 1 2 1
Reactions of organogold(II1) complexes . . . . . . 138
Carbene complexes of gold . . . . . . . . . . . 144
Alkene and alkyne complexes of gold . . . . . . . 148
References . . . . . . . . . . . . . . . . .151
C'hapter 8. C o m p o u n d s with G o l d Metal B o n d s
Gold-gold bonded complexes . . . . . . . . . . 157
Gold cluster compounds . . . . . . . . . . . . 160
Alloys and ligand-free gold-metal bonded compounds 1 6 4
Compounds with gold main-group-metal bonds . . . 165
Compounds with gold transition-metal bonds . . . . 169
References . . . . . . . . . . . . . . . . . 176
Chapter 9 . Reaction "Plechanisrm in Gold Chemistry
Ligand substitution reactions in gold(1II) complexes . 179
Substitution reactions in gold(1) complexes . . . . . 193
Electrophilic substitution reactions . . . . . . . . 194
Homolytic substitution reactions . . . . . . . . . 200
Oxidation of gold(1) complexes . . . . . . . . . 201
Reduction of gold(II1) complexes . . . . . . . . 203
References . . . . . . . . . . . . . . . . . 208
Chapter 1 0. Spectroscopi c. Studies of Gold C o m p l e x e s
Vibrational spectroscopy . . . . . . . . . . . . 210
Nuclear magnetic resonance spectroscopy . . . . . 223
Mossbauer spectroscopy . . . . . . . . . . . . 226
Nuclear quadrupole resonance spectroscopy . . . . 234
Photoelectron spectroscopy . . . . . . . . . . . 234
Ultraviolet-visible spectroscopy . . . . . . . . . 236
References . . . . . . . . . . . . . . . . . 240
Chapter 11. Analysis and Applications of Gold C o m p l e x e s
Analytical methods for gold . . . . . . . . . . 243
Biological applications of gold . . . . . . . . . . 247
 Catalytic properties of gold . . . . . . . . . . .253
Methods of gold coating . . . . . . . . . . . ,256
Other applications of gold . . . . . . . . . . . 257
References . . . . . . . . . . . . . . . . .257 lNTRODUCTlON TO T H E CHEMISTRY OF GOLD

Appendix
Gold-element bond lengths . . . . . . . . . . . 261 In this chapter we shall consider first the occurrence of gold
References . . . . . . . . . . . 267 and the ways used to extract and purify the element from its
ores. After this, the properties of elemental gold will be covered,
Subjectlndex . . . . . . . . . . . . . .270 followed by a preliminary survey of the oxidation states and
stereochemistri~sadopted by gold in its complexes. Finally,
some general concrpts which are useful in interpreting and
rationalising the properties of gold and its complexes will be
introduced. It is hoped that, using this general framework, the
reader will be able to place the detailed properties of individual
gold complexes, which are treated in subsequent chapters, into
their proper perspective.

OCCURRENCE O F GOLD

From studies of the solar spectrum the abundance of gold

in the sun is found t o be 0.04 parts per million (ppm), but in
the Earth's crust it is on average about 0.004 ppm. Thus, gold
is probably more abundant in the core than in the crust, where
concentration by a factor of about 1 0 3 is necessary before
economic extraction is feasible.
Concentration of gold, which usually occurs in nature in the
metallic form, has occurred in two ways. The first gives rise to
alluvial or placer gold, and consists of the weathering of auri-
ferous rocks which have been washed into river beds or similar
situations. The greater specific gravity of gold (19.3) compared
with residual rock (- 2.7) leads to gold settling out while lighter
rocks are washed away. Alluvial gold, once discovered, is often
easy to extract as nuggets or grains by simple gravity concentra-
tion and the sources which gave rise t o the great gold-rushes
of California in 1848, Australia in 1850 and the Yukon in
1 8 9 6 were of this form. Much of the gold found in the lJral
mountains of the t1.S.S.R 1s also alluvial gold
The greatest gold fields are those in South Africa, where the
gold o w u r s as thin veins in quartz rocks. Thc gold, known as
vein or reef gold, IS present as micmscopic part~clesso that
extraction is considerably more d~fficultthan for alluvial gold.
In general reef gold 1s found In quart^ o r a l h ~ t rocks,
t often
along with irotl pyrites D t q ~ ) s ~wltht s silvt)r and other rare
metals often o w u r in volcanic rclgions c.ontrollcd by nialor fault
zones. Itere, cSoncentratlonof the gold takes place hy hydro-
thermal metamorphism frvrn bas~crocks dtid tlryosition ln
s t d ~ n ~ c n t a rorks
ry 11 2 1 (;old :s ( onsidtrtvl to hr) an mcrt
n~c$al but ~t (,an bv d~ssolvcdyuitr rc~atlllq halld(1 or >ull)hidtl
~ o n in
s the presence of ouidlslng agents to g i v ~gold(if1) or
goid(1) conlpleut~s.It 1s prohal-)ly in thli way that gold is dis-
solved when hot volcanic rock 15 hurled o r when a h o t granitt.
rntrusion riws n f w t o t h iurfarr
~ of thc Fhrth's crust Stud1r.s
of model systt.m~suggest that i f the oxygen rani-clntration is
governed tly t h tlqu~hhrium
~ The gold fields o f South 11 fr1c.a h a w so far y lelded over 3 1
and the chloride concentration and pH by the mica feldspar
quartz buffer system, then a t the high pressures and tempera-
tures o f 400-600 "C which are likely, gold would dissolve ulu
reactions of the typtx:
As the solution cools t o 300--400 "C the concentrations o f
oxygen and o f HC1 are expected to decrease sharply, and gold
is redepcsited. The nature of the deposit will obviously depend
o n t h e precise conditions, and o n the nature of the convection
patterns or percolation routes of the cooling solutions. Hydro-
thermal transfer of gold as the complex ion [Au(SH), ] - may
occur in some cases [ 2 b ] .
* There is n o direct evidence for the existence of H3AuCI,. H[AuC14] is
perhaps more likely.
Dissolution and redeposit~onof gold in stream beds may
ilso be responsible for the formation of large crystals of allu-
L ial gold. Particularly mteresting is the observation t h a t some
micro-organisms and then- metabolites isolated from gold-
learmg deposits are capable of dissolving gold. The maxlmum
i~ssolutionof gold by isolated bacterial metabolltes studied
W far is 10-35 g m - ' in 20 days. Ilissolution is aided by t h e
,)resence of aspartic acid, histidinc, serinc, a l a n ~ n eand glycine
ind by metal oxidants [ 3 ] .
The only compounds of gold which form important minerals
.m the tellur1dt.s. Examples include calavwite and krrnnerlte,
wh1c.h are dlffcrent crystalline forms of AuTc?, m o n t h r a y ~ t e ,
,,
Zuzrre and m ~ r e dg o l d - s ~ l v ~tellurides
r such as sylvanite,
\uAgrI'e, Nat~vc.gold also contains sllver m varying propor-
tlons, one well-knowt~rxamplv hcmg clcctrum with about
20% silvcr. Uther v a l u a b l ~txlcmcnts obtained as m m o r constl-
t ~ ~ c nfrom
t s gold ortls a t . ~ridlum,osmium, platinum, rhodium,
ruthenium and palladium as wrlll as cwppr3rand nlckel.
million kg of gold, wh1c.h is m o w than half thc gold reserves
of the world. The second largest producer is the U.S.S.K. but
the precise amounts mined thew are not put)l~shtd.No other
country produces comparable q u a n t l t ~ e sof gold, b u t Canada,
thc U.S.A., Australia and othcr African and South Amcrican
countries still product, significant amounts.
The presence of dissolved gold in sea water was discovered In
1872, and many uniformly unsuccessful attcmpts have been
made t o recover thc gold cornmcrcially. The most famous
attempt was made by Fritz [laber, with the intention of paying
off the German war debt, in the years 1920-1927. The method
was based o n reduction t o metallic gold using sodium poly-
sulphide, but the available estimates of the gold concentration
in sea water were t o o high by a factor of about 1 0 3 and t h e
results were all disappointing. Most other methods rely o n
adsorption o f gold on various media, including rc.c.cntly poiy
mers contaming t h ~ o groups l which coniplm strongly to go11-1,
Some of these methods are useful in concentrating gold, so that
accurate analyses can be pcrformc.d, and ~t is now thought that
the concentratlon of gold In sea water 1s about 2 x 10 " 11,
though the c~oncentrationfluctuates dcpenc-ling on t h e gro
graphic region and depth from w h ~ c hsamples arc6iwll~cttct
15. 61 I t thcsc low c*onccntration~, ~t is not possiblt. t o d t t w
mine clirt.ctly t h c nature of the gold spcc~csp r r v n t , hut c.,ilc,~la-
tlons hastd o n redox potent~alsof gold compounds dnd t h ~
t w n ~ p o s ~ t i oo nf sc.a water suggvst that tho gold( l ) c~)mpltt\cIon
l i~rtbd~)riltl~~itt'n.with bnl,~llt,r, m o u n t \ o f I \uC'IRr 1
m d c~thorI)rorno, loci0 ,ind tiytlroxo c.otr~~)lc~\ ~ ( I I of
I ~ gold(l)
17 1 nlso hc>~ng prtwnt
Rt~covcrqof gold from ,illuv~aldtyoslts by gravity conc cwtra-
tion dates bach a t lcast 6,000 yc1~lr\ I'hc g o i d - c ~ ) n t a ~ n matcw;il
~ng
was c*cinvcqrd watcbr d o w n , I \11i1( P ( q u ~ p p rwith
~ l transvcrw
r~ffleswhlch trapped the heavier gold particles. It 1s thought
that the use of animal hldes in this prowss gave rlse t o the Iegtwd
of the Goldcn F l t w ~of Jason and the .Irgonauts. A11 Improve-
mrbnt to the. method was dwt~1o~)r.d wh1c.h ~nvolvcdthe use of
mrxrc,liryIn tht. nfflrs t o amalgamatil the stttling gold partlclc~s,
the gold kwing re( ovcrrd by distilling off the rnc3rc.uryin retorts
and thc gold f~nallysmt>ltrtl
'I'hesr. mcthods arc. u n w ~ t a h l tfor
~ h ~ g hyic'ld rccwvery of
reef gold in wh~c-hthe gold con(-entratlon may hc only 1 0 ppm
o r less, and the Following is a typical modcrn procedure. The
ore 1s first crushed and then mllled t o give the fine particles
needed for efficient extraction. Part o f the gold 1s still recovcrcd
by the gravity concentratlon, amalgamation, retortmg and
smeltmg procedures whlch have been much ~ m p r o v e dby modern
technology. The tailings from this process are not discarded
however, b u t are treated with a l k a l ~cyanlde and compressed
air t o dissolve the gold according t o the equation:
The solution is filtered t o remove the gangue and the gold is
rcprecipitated with zinc:
Recovery of gold w ~ t han efficiency of around 98% can be
~ c h i t v e dusing thls combined method, with the product from
the fmal s m e l t ~ n gprocess containing 88-90% gold. The resi-
dual constituents are silver (-10%) and small amounts of copper,
lead, zinc, Iron and platinum group metals.
Most gold IS p u r ~ f l e dby t h e chlorination process. Chlorine
gas is bubbled through the moltcn gold and t h ~ converts s
,ilv(lr and haw mc>talst o t h t chlorides which float t o the surface
nnd can be removcd r a s ~ l y Gold . o f purity 99.5% 1s produced
In this way and, ~f n c ~ ~ s s a r 1s y ,further rcflned by elt~ctrolysls.
I'he anode is thc crudcl gold, the r.lec.trolyte IS kI[AuCI41 in
hydrorhlor~cacid, and the cathode is pure gold. Pure gold is
dcpositcd a t t h e cathodc, whdc platmum and pallad~umcan
1)e rccovc3red from the anodcx mud.
A convenient method for the recovery of gold from gold
rc.slducs In the laboratory consists of pyrolysis of the r w d u c q
followtad by dissolution o f the gold In nquu rr.gla. The pII IS
adjusted t o p11 2-4 by addmg s o l d sodium h y d r o x ~ d and t the
gold is reprcclpltated uslng sodium s u l p h ~ t eas reducing agent.
12 slmllar procwlure can bt. uscd t o obtam gold powder from
m&ssivc>gold.
Gold is perhaps the most bwutiful of thp chemical elements
and has been known and treasured by man sincc t h e earliest
times. In the massive form it is a soft, yellow mctal with the
highest ductility and malli~abilityof any element; thus one
ounce of gold can be beaten o u t t o 300 square feet. Gold has
an atomic weight of 196.967 and a density a t 2 0 OC of 1 9 . 3 2 g
cm-'; the pure metal melts a t 1 0 6 3 "C and boils a t 2966 "C. T h e
beauty and rarity of gold has led t o its use in jewellery and in
coinage and as a standard for monetary systems throughout
the world. Since gold is such a soft metal, it IS usually alloyed
t o give it more strength. In thesr alloys the term carat is used
to express the amount of gold present, 24 carats benlg pure
gold. Alloys of gold with the other elemcnts of group I B are
most frequently used. Thus, colnage gold typ~callycontains
10% copper, while gold used in jewellery and dent~strymay
contain varylng proport~onsof silver and copper. The colours
of the alloys are frequently controlled by the other metal.
Thus, an alloy c-ontalning 50'4 copper is dark red, and one
conta~ning65% s~lvcris w h ~ t xand hardly d~stinguishableto
tht, i5yt>from pure s~lvcr.Thcb whlti, gold cornrnotily used In
jcwtlllcry contains 75--85S gold, w t h 8 10r; nnlckt.1 and
2 9": ~ m cw, h ~ l enorcl cxpt\nsivt1whlte alloys art1pallad~urn
gold (90% Au, 10% Pd) and platlnurn- gold (60% A u , 40% Pt).
Gold also has h ~ g hthern~aland i.l(vtr~calconductiv~ty;hence
its use In electron~cs.The high cost of gold necess~tatrsthe use
of very thm films, f o r m d by c.lrc.troplating o n a base metal
support, for gold switc.hmg dcviccs
Like the>other group [B clemrnts, gold crystallises in thc
face-ccntrcd cubic lattice. and the closest iritcr-nuclt.ar d~stance
is 288.4 pm.
At high temperature in the gas phase, gold exists as a mixture
of atoms and dmtomic molecules. The d~ssoc~ation energy
( D o " )of tlu, is 2 2 1 + 2 kJ mol-'and the . \ U -Au bond length
is 250 pm 1101.
COLLOIDAL CiOLL)
Solutions containing gold complexes such as [AuCl,] are
easily reduced to gold, and under controlled conditions coll-
oidal gold may be formed. Colloids of gold may be red, blue
or violet depending on the mean particle size and shape and
have been known for a long time, certainly since the 18th
century. Various reducing agents can be used for preparing
colloidal gold, some of the earliest being tannin and phosphorus,
while the "potable gold" of the alchemists, t o which fabulous
medicinal powers were attributed, was obtained by reducing a
solution of gold in aqua regia with ethereal oils. Formaldehyde
and hydrazine hydrate are now commonly used as reducing
agents. Particularly important is the "purple of Cassius" which
has long been used as a colouring agent for enamel and glass.
This is thought t o be a mixed colloid of hydrated tin(1V) oxide
and gold formed by reducing [AuCl,]- with tin(I1) chloride.
.2 purple or ruby-red precipitate is formed on heating the solu-
tion. This forms the basis of a sensitive test for gold; thus, the
purple colour is formed if a 10-8 M solution of [AuCl,]- is
added to a saturated solution of tin(I1) chloride.
!SOTOPES O F GOLD
Gold has an atonuc number of 79 and an atomic weight of
196.967. Thus, the nucleus of the only stable isotope I 9 ' ~ u
contains 79 protons and 1 1 8 neutrons. Details of the other
known isotopes of gold are given in Table 1.1.
The neutron-deficient isotopes are prepared by bombarding
lighter atoms with positively charged particles in a cyclotron or
linear accelerator The ~sotopesof mass numbers from 1 7 7 t o
183 are all alpha emitters and all have half-lives of less than one
rnmute, while those with mass numbers of 185-196 decay by
electron capture accompanied by gamma radiation and in some
cases by positron emission. Of these isotopes the only long-
lived one is ""Au with a half-life of 1 8 3 days; this isotope is
prepared by the rrac'tion.
' ; ' ; ~ t+ ; p - ':;;.\U + ;)l,
A target of platinum (which in natural abundance contains
33.8% """t) is bombarded with 22 MeV protons in a cyclotron.
This is an exptwsive process made yet costlier by the need for
subsequent sclparation of gold from platinum; hence '"AU is
not widely ustvi.
The neutron-heavy isotopes are prepared by neutron capture
reactions, and all decay by p-emission accompanied by gamma
radiation. The most important isotope in this group is I o s ~ u ,
which is prepared in a nuclear reactor by the reaction:
';:Au + An + Au
 This is a particularly favourable reaction since 1 9 7 ~ the
u,
TABLE l . la only naturally occurring isotope, has a high neutron capture
cross-section of 98.8 barns. Thus, with a moderate neutron
The Isotopes of Gold
- flux of 2 X 1013 n cm-* S-', a specific activity of 1 curie per
Mass No h Half life Vode of decayC gram is obtained in 6.5 hours. The isotope '"AU is widely
---
lsed in radiotherapy, in medical diagnosis and for tracer
177 135s Q ,tudies.
178 2.65 s Q
179 7 25s Q
181 11 5 5 c U, EC CtIEhIICAI, REACTIVITY O F GOLD
183 25 5 S N
(;old is the most noble of the metals, being the only one
185 4 3 rnln a , EC
186 12 m111 l?<', y
which is not attacked hy either oxygen or sulphur a t any temp-
187 X mln cr, KC erature. Gold does howtwx react with tellurium at high tempera-
188 8 mm EC, y turcs, to give AuTc,, and reacts with all the halogens. Of these,
189 29 7 mm E(', y hrorninc. is the most reactive and reacts exothermally with gold
189m 17 mln EC, y powder at room tempcmture t o give Au,Br,. The reaction with
190 39 min EC, y ci~lorinchas been studied in more detail due to its application
191 32 h E(', y
192 5 0 h E(:> 0 +, 7 in thr. purification of gold. At temperatures below 130 "C,
193m 395 Y chlorine is adsorbed onto the surface and then forms surface
193 17 5 h KC', y conlpou~ds;at temperat~1rc.sbetween 130-200 "C, further
194 39 5 h E(',p+, 7 :cmtion can take place but the rate is limited by the rate of
195m 31 0 s p+> Y Jiffusion of chlorine through the surface layer of gold chlorides.
195 1 8 3 day EC, y
196m 97h '7
i ) ~ l above
y 200 "C is a high reaction rate achieved as the gold
196 6.2 day EC, /j, Y chlorides then sublime, thus continually exposing a clean gold
197m 75s Y surfacc. [ 111.
197 hLdble
(;old will dissolve in aqueous solutions containing a good
Izgand for gold and an oxidising agent, but neither condition
198 2 70 day it Y alone is sufficient. Thus, gold will not dissolve appreciably in
199 3 1 5 day 0, Y
200 48 4 miri 8, r hydrochloric or nitric acid, hut dissolves readily in aqua regia
201 26 min 0, Y t o give t,ctrac:hloroauric(III)acid, H[AuCl,]. Similarly, gold
202 30 S 0.y ill dissolve in hydrochloric acid in the presence of hypochlo-
203 55 S 0, r r'lte or iron(ll1) as oxidant. The dissolution of gold in cyanide
204
-
4 05 S B, r -01utions with air or hydrogen peroxide as oxidant is another
a F r o m : L. Myerscough, Gold B u l l , 6 ( 1 9 7 3 ) 6 2 m = metastablc. example of this effect. The reaction with oxygen as oxidising
C a = alpha emission, EC = electron capture, P+ = positron emiss~on, agent apparently takes place by adsorption of oxygen onto
B = beta particle emission, y = gamma r a d i a t ~ o n . the gold surface, followed by reaction of this surface layer
with cyanide t o give first AuCN and then the complex
[Au(CN),]- which passes into solution.
 Atomic gold is considerably more reactive than the massive
metal. Reactions of atomlc gold can be carried out by evapora-
tion of the metal at high temperature under vacuum and then
co-condensing the gold vapour with a suitable reagent onto an
inert noble-gas matrix at liquld helium temperature. In this way
the complexes mono-(dloxygm)gold,A u ( 0 2 ) ,and tnono(ethy-
lene)gold, Au(C2hI,), and the carbonyls Au(CO) and Au(CO),
can be prepared and ~dentlfledspectroscoplcally. Co-rondensa-
tion of atomic gold with carbon monox~deand dloxygen qves
the complex
whlch 1s thought to be involved in the gold-catalystd rcactlon
of CO and 0; to give CO,. ,411 these gold compounds dec-om-
pose on warming the matrix [ll b 1.
OXIDATION STATES O F GOLD AND THE STEREOCHEMISrrRIES
O F GOLD COMPLEXES
In complexes containing a single gold atom, the oxidation
states I, 11, I11 anu V are well established and gold also forms
many complexes with metal--metal bonds in which it is diffi-
cult t o assign formal oxidation states to the metal atom. Gold
has the electronic configuration [Xe] 4fi45d"6s' and
belongs t o group IR af the periodic table along with copper and
silver. In this section, we shall study briefly the nature of typical
complexes of gold in each oxidation state so that comparisons
with the other group IB elements can be made, and a detailed
treatment will be found in subsequent chapters.
(a) Oxidation state 1
Of the group IB elements, silver alone forms a simple aquo
ion in oxidation state I. Gold(1) and copper(1) compounds
disproportionate in aqueous solution unless they are either of
very low solubility (e.g., AuI) or strongly complexed (e.g.
[Au(CN),]-) according to the equations:
2Cu(I) + Cu + Cu(I1)
3Au(I) + 2Au + Au(lI1)
Since Au' has the closed shell electronic configuration [Xe]
4fI45d", gold(1) complexes are diamagnetic and adopt regular
structures. The most common stereochemistry is linear, the
co-ordination number of the gold atom being two [12-141,and
such complexes may be cationic such as [Au(PPh,),]+, neutral
such as [Au(CN)(PPh,)] or anionic such as [AuCl,]: In this
respect gold(1) differs from silver(1) and copper(1) which have
a greater tendency t o form complexes with higher CO-ordina-
tion numbers. Thus, the complex MI(PEt,) is monomeric when
M = Au, but exists as a tetrarner [ { MI(PEt,)},] with bridging
iodide ligands when M = Cu or Ag, so that the metal atoms have
co-ordination number four. Higher co-ordination numbers are
also known for gold(1). Thus, trigonal planar complexes [12,
151 wlth co-ordination number three such as [Au(PPh,),]+ and
[AuCl(PPh,),], and tetrahedral complexes [l61 with co-ordina-
tion number four such as [Au(PMc,),Jt are known but these
readily lose phosphine ligands and revert t o the more favoured
linear two co-ordinate form. We shall consider later in this
chapter possible explanations for this relative preference of
gold(1) for co-ordination number two when compared with
copper(1) and silver(I), and the similar effect observed in group
IIB, where mcrcury(I1) forms many linear two co-ordinate
compounds but zinc(I1) and cadmium(I1) d o not.
( b ) Oxidation state II
The oxidation state two is dominant in the chemistry of
copper, but considerably less common for silver and very rare
for gold. Thus this oxidation state is established for gold only
in the following situations:
(1) There is strong evidence that gold(I1) species are formed
as transient intermediates in redox reactions between the stable
oxidation states I and I11 [17].

( 2 ) Stable gold(lll zpt>cit.s may be l o r r n ~ d111 wh1c.h t h t w is
a gold- gold bond .An c~xan~plt~ is g1vt.11in Fig. 1 1 ( 18 1.
( 3 ) With certam un5atr1r;itc~isulphur-donor I~gandsSLI( h as
maleo11itrlled1thioli1te 1011, milt' , sola able cwrnplc\t.s of gold( 1 1 )
such as [ A u ( n ~ n t ) ~ with
] a square planar four cw-ord~nate
gold(I1) centre as shown below may he fornitd.
In gold(I1) complexes the metal has the 5d" configuration and
such complexes are expectcd to he paramagnetic unless thcw
IS a gold-gold bond. Monomeric gold(1I) compltxes w ~ t h
dith~olateand dith~ocarbamatel~gandsappear t o bc ,tabiliscd
by delocalisation of the unpaired clwtron over the unsaturated
ligand [19].
( c ) Oxidation state I l l
This is an important oxidation state for gold but is rare for
copper and silver. All known gold(II1) complexes are diamag-
netic with the low-spin 5dHelectron configuration, and the
vast majority of these compounds have the four co-ordinate
square-planar stereochemistry. Examples include the complex
ions [AuC14]- and [Au(NH,),] 3', but the simple aquo ion
[Au(OH,),] " is never formed even on dissolution of gold(II1)
hydroxide in nitric acid or sulphuric acid [20]. Five co-ordinate
gold(II1) complexes are rare, but when formed they are square
pyramidal or distorted square pyramidal, as in [AuC1,(2,2'-
:,iquinolyl)] and [AuCl, (2,9-dimethyl-l, l 0-phenanthroline)]
vvith rigid bidentate nitrogen-donor ligands [21]. There is
~videncethat the complex ion [Au(diars),I] ,+,where diars =
1.2-his-(dimethylarsino)benzene,is five co-ordinate but its
,tructure is unknown. Trigonal hipyramidal gold(II1) complexes
ire generally invoked as intermediates during ligand substitu-
8 ion rrwkions In square planar gold(II1) complexes. In co-ordi-
dtion number six, a tetragonal stcreochemistry is always
~ssumt.d[22] and has been proved for [Au(diars),I,]'. The
-1tuatlon may be comparcd wlth that for [ c u F , I 3 and [AgF,13
wh1c.h are paramagnetic w ~ t hp c , , 2.8 B.M. and 2.6 B.M.,
wspectively, at room tempcraturc; these coniplex ions presum-
ihly have regular octahtdral structures. Howcvvr, all other
( ' ~ ( 1 1 1 and
) Xg( 111 on~poundhare diamagnt3tic. with square
&mar co-ord~nat ion
* d ) Oxidation state V
'I'hc first gold(V) complex containing the ion [AuFJ was
reported in 1972 by Bartlett and co-workers. It is diamagnetic
and has a regular octahedral structure with the low spin 5d6
electronic configuration [ 2 3 ] . The compound AuF, can also
be prepared. These compounds are very powerful oxidising
agents, and no analogous compounds of copper and silver are
known.
From the foregoing account, it will be clear that there are
more differences than similarities between the properties of
gold compounds on the one hand, and of either copper or
silver compounds on the other hand. In many cases, it is more
valuable t o make horizontal comparisons of gold with the
neighbouring elements platinum and mercury in the periodic
table than with the other group IB elements. Thus, isoelectronic
species such as [AuC12]- and [HgCl,], [Au(PPh,),]+ and
[Pt(PPh,),], and [AuCl,]- and [PtC1,I2- exist. In the following
sections we shall attempt to rational~sesome of the similarities
and differences between gold and the other group IB elements,
and to study the factors which affect the relative stability of
the common oxidation states ( I ) and (111) in gold complexes.
IONISATION ENERGIES AND ELECTRON AFFINITIES O F TIIE
GROUP IB ELEMENTS
The factors governing the stability of oxidation states of an
element are of course complex, and cons~drratlono f cornplcte
energy cycles 1s desirable. Ilowever, Lhc required data are ~ i o t
available for many compoulids, so that we are driven to use
criteria such as lonlsation enthrglcsand electron affinltles as a
general guide. These are given In Tablc 1 2 and are particularly
useful for the group IB elements.
TABLE l . 2
Element 1st 2 nd 3rd 4th
It is worth noting that the first ionisation energies are con-
siderably higher than for the alkali metals (e.g., K, 419 kJ mol ' )
The ionisation process for potassium is K { [Ar] 4s' l + whether copper(1) or silver(1) has the greater tendency t o linear
K+ {[Ar] 1, while for copper it is Cu {[Ar] 3d"4s1 1 -t
Cu' {[Ar] 3dI0}. The outer 4s electron feels a higher effective
nuclear charge in copper than in potassium because the increasrd
nuclear charge in copper is not balanced due to the poor shield-
ing by the electrons in the diffuse 3d" subshell. The first
ionisation energy for silver is lower than that of copper due
primarily to its greater atomic radius, but there is a large
increase for that of gold whose electronic configuration is
[Xe] 4f'45d106s1.Here, the outer 6s-electron is poorly shielded
from the nuclear charge by both the 4f and 5d electrons, so
that it feels a high effective nuclear charge. It is a combination
of this high ionisation energy and the high binding energy
which gives gold its noble character.
Variations in the second and third ionisation energies are
also noteworthy. Thus, the relatively high second ionisation
energy for silver accounts partly for the dominance of the + I
oxidation state for this element, and the relatively low third
ionisation energy for gold leads t o the + I11 oxidation state
being preferred. Subsequent ionisation energies are also lowest
for gold, no doubt explaining the existence of the + V oxida-
tion state for gold b u t not for silver or copper.
Accurate valur.s of the clcctron affinities of the group IB
clrments are difficult to obtain, but there is general agreement
that gold has the highest value. Values of 226 and 270 k J mol-'
have bcen proposctl by different workers 123, 241. These
rrbtivdy high va1uc.s have promptr.d the suggestion that gold
may he considcwct as a pseudohalogen [cf., E.A. for iodine is
296 kJ mol-'1 and there is indeed evidence that the compound
CsAu may be cwnsidrwd to be CS' Au-. Certainly gold is
expected t o have a high electronegativity on the basis of its
high ionisation ttncrgy and electron affinity.
CO-ORDINATION NUMBER IN (;OI,Il(I) COMPLEXES
As mentioned c a r l ~ ~gold(1)
r, complexes have linear two co-
ordinate stcreochemistry much more commonly than copper(1)
or silver(1) complexes. Thrre has been some debate about
co-ordination, and this may be dependent on the ligand t o some
extent. The tendency to form linear complexes can be measured
by the relative magnitudes of the second and third stability
constants. Thus, for the cyanide complexes the ratio of log P,/
log P, is for Cu(1) 1.25, for Ag(1) 1.11 and for Au(1) 1.00, so
that in this case the tendency to linear complex formation is
Au(1) > Ag(1) > Cu(1). The factors responsible for this sequ-
ence are not clearly understood and several theories have been
put forward.
 Firstly, it can be said that steric factors are unlikely to be the p-orbitals of copper and silver, which are at relatively low
Important when considering two- and three-co-ordinate com- imergies.
plexes, so that electronic factors must be responsible. Consider- A third theory is based on the Ligand Field theory of bond-
mg only smple electrostatic effects, a metal ion with a high ing [27, 281. Thus, in a linear complex with the ligands lying
polarising power should have a high co-ordination number. dong the z-axis, it may be favourable t o hybridise the filled
Thus, for the group IB metals in oxidation state I, the order td,z and vacant ( r l + 1 ) s orbitals. This will give one orbital
should be dependent on the ionlc r a t h wh~chare C'u' 81 pm,
.?\gt 126 pm and Au' 137 pm This g~vrsthe mrrect serles,
b u t would wrongly p)rcti~c,t3 c4owr iirn1lar1t-yof sdvw to gold
rather than to cwpper
'2 sec oild t,htwry curisrdi.rs t h e n,it u r t ~o t t h(, o r b ~ t d su s ~ i
:.l t)ordi:ig I'hus ,p 11) h i d j r h i t d , will I N i t ~ 111 d 11ne,u

Fig. 1 . 2 . f I y b r i d i s a t ~ o nsrhrmc* I'or goltl(1)

complrxc~s,sp2 hybrid orbitals in trigonal planar complexes

and sp3 hybrid orbitals in tetrahedral complexes. The ease with
which hybridisation of s and p orbitals takes place will depend ' ' 1 ~ . 1 . 3 . tIy1,ridisation o f :)d,2, 6 s a n d 6 p o r t ~ i t a l s (
. a) formation of
on the energy separation between these levels. This is illustrated ,
*iyl,rid orbitals $ a n d I)] rtnmoving r ~ l c c l r o ~ density
i i n t o $ away f r o m
!Ire ---axis, ( h ) formation of linear bonding hybrid orbitals f r o m $ 2 and
in Fig. 1.2. . E. Huheey, Ir~orgclrr~c.
'<pi o r l ~ i l a l s (J. ('hc~~rllslry, Harper a n d R o w ,
The rzs-tzp separations for Cu, Ag and Au atoms are 3.79, i,ondon, 1975, p. 372).
3.66 and 4.63 eV, respectively. Thus sp hybridisation rather
thar, sp2 01. sp3 hybridisation is expected to be more favour- w ~ t hmaximum electronic density in the xy plane and one with
able for gold than for copper or silver, since the higher s-p maximum electronic density along the z-axis as illustrated in
separation will make hybridisation of s and p orbitals more Fig. 1.3.
difficult [26]. The same conclusion is reached if the bonding Now, if the electron pair is in +,
rather than the d12 orbital,
is considered in terms of Molecular Orbital rather than Valence there will be less repulsion between the electron pair and the
Bond theory since the p orbitals of gold are at relatively high ligands, and the complex will be stabilised. This is a second-
energy, and therefore less likely to take part in bonding than order ligand field stabilisation energy. The orbital $, will
hybridise with the (n + 1 ) p orbital t o form two linear hybrid where .rr" is the standard electrode potential (estimated [25]
orbitals to overlap with the ligand orbitals and so give a linear to be +1.7 V though a value of 1 . 8 3 V has also been suggested
complex. This d s mixing will again become less favourable as [29]). This then reduces to (IT in units of volts):
the d--S separation increases. The energies of the lowest d9s
state above the d i Oground state are for Cu' 21,928 cm-',
.rr = 1.7 + 0.059 log,, [Au' l
Ag' 39,164 cm-' and Au' 15,039 cm-'. Thus, the second- It is possible t o derive similar expressions for alternative
order ligand-field stabilisation energy on formation of linear oxidation processes [30] :
complexes is expected to follow the series Au' > Cu' > Ag'. Au -t i4u3+ + 3e; .rr = 1.50 + 0.0197 log,, [AU"]
Thus, again gold(1) is correctly predicted to have the greatest
preference for linear co-ordination, but the prediction that
copper(1) should resc.mblt~gold(1) more than silver(1) is not
upheld.
The predictions of the three theories can bc sun~marised These reactions can only take place if sufficiently strong
in terms of the ttlndency to form linear cwmplexes: oxidants are prtwnt, and reactions in aqueous solution are
(1) Polarising power of M ' predicts Au(l) > Ag(1) 3 Cu(l) further limited by t h e limits of stability of water to oxidation
( 2 ) s-p energy separation predicts Au(1) 9 C:u(I) > Ag(1) to oxygen, or reduction to hydrogen.
( 3 ) d- s energy sepearationpredicts A u ( l ) > Cu(I) 9Ag(1) The system can hc cxrwssed graphically in the Pourbaix
diagram in w h ~ c hthe cc~u~librlum potential of each couple 1s
Thus, if all threr. effects are apprcciablc, a combinetl predic-
-
tion Au(1) S Ag(1) Cu(1) m ~ g h be t deduced, in agreement
with experiment. It is, however, difficult to estimate the wla-
tive importance of the three c.ontributions.

OXIDATION-REDUCTION POTENTIALS

( a ) The aqueous chemistry o f gold

OH
To understand the nobility of gold, it is useful to consider
the redox potentials of gold in the absence of co-ordinating 0
U --_
04
ligands. Thus, for gold to react it must be oxidised, e.g., 8 AU

Au'(aq) + e-
Au
--a-..
L
+
04
The tendency for this reaction t o take place is given by the ..._
Nernst equation: 0 2 4 6 8 pH
1 0 1 2

RT Fig. 1 . 4 . Pourbaix diagram for the system Au-H20 at 25 'C. The

.rr = .rr" + 2.303 - log,, [Au+]/[Au] concentrations of all gold species are 1 0 - M.
~
F
plotted against pH for particular concentrations. A simplified
Pourbaix diagram for gold (using a concLentrationof
is shown in Fig. 1.4 and indicates the conditions under which
particular species are expected to be formed [311. The mean-
ing o f the diagram becomes clear, once it is realised that the
dotted lines ( S ) and ( 2 ) represent the lim~tso f stability of
water Now the o\idistd forms of gvld cxlst only at potentials
greater than for line (1). lTnderthew cond~tions,water will
be oxldised to o x y g ~ nand thc~v a r i o ~ ~oxidised s gold species
will he reduced to gold metal. l'hus, In the absence of 00-ordinat-
~ng Ilgands, gold cannot i-,r o\iltl~ardb y ihssolvtd oxyge~lm
ihe presenc't. o f t,!thitr ~ t r l , r ~.icg~ d ~s ), trr # ) n g a l k , h (;old i s
h.only rni>t,~lfor whlc h thls 1 5 tht. abcl. .urd i i 11.111, tr~11)tht,
most noble o f t hc mctall~celcmcwts
Thus, In the presence of a good ligand L for gold(I), a high
M) value of K and a low value of (T* )' will be obtained. Some
typical standard potentials are given in Table 1 . 3 [25, 29-34].
Values corresponding to equation (S) are termed T,: to indi-
cate that they refer to oxidation of Au(0) to Au(1). The order
,,
of decreasing TT is then the order of increasing stability of
the compl~xes[AuL,]'. Note in particular, the low value of
,,
TT for oxidation of gold in the presence of cyanide. It is this
case of oxidation of gold in the presence of cyanide which
makes the cyanide process for the extraction of gold feasible.
S t a n d a r d r t d o x potclnti;ils(V) I'or g o l d in a q u e o u s solut.ion
-. **
1,ig;ind . n1.0 11.0 n.3. I

fI20 + 1.7 + 1.50 t- 1.4

The wason for the high electrode puttwtials for vxidation (+2.12)
of gold in the :ibsenw o f ( omple\ing Iigands 1it.s i n the vwy Cl +l.l5 + 1.00 + 0.93
low ,tahilit> o f ihc~~ l y u u~ c r l i s[,4u(OH, ),l and [.Zu(OH, ), I I f
+
Br + O 9G + 0.8 6 + 0.8 1
I + 0.5 f; + 0.5 7 + 0.57
The potentials are lower in the presence of complexing ligands. ~

S(:N- +0.67 +O.G +0.62

Thus c-onsider the equilibrium in the prcsclnce of a ligand I,. NI-1 t0.563 +0.325 +0.206
thiourra C0.38
selenourea + 0.20
CN- 0.61
Sul~stitut~ng
111 thc. Nernst cquatlon uscd prcuously the
cyuillbr~umc'oncentrat~onfor [Xu(OH,),1' i n the prPsrnw
of chlor~de,we find. I t should be realised, however, that the standard pottsnt~nls
only tell us that the rractlon is feasible thermodynamically.
Whether it takes place readily or not, wlll depend on kinetic
factors.
I t is, of coursc, possihlc to oxidise gold to gold(111) in the
presence of suitable ligands :

Again, the standard potentials nz, will depend on the stability

where (T-)l is the standard electrode potential for the couple:
constant for formation of the complex [ A U L ~ ] ~Typical
'. values
Au + 2L [AuL,]' + e- (1) are given in Table 1.3.

From the forego~ngdisc*ussion. it will br. clear that both
gold(1) and gold(II1) form m o w stablv complcxcs w ~ t hI than
with BY, and with Hr- than w ~ t h('l . Thus, In both common
oxidation states gold 1s a "class h" metal or a "soft a d , "
preferring t o bond t o large polarisable ligands. LVe have also
seen that gold(1) d ~ s c r ~ n ~ i n amore
t e s than gold(II1) between
hard and soft ligands so t h a t gold(1) may be considered t o be
the softer metal ion*. Copper(1) and silver(1) are also soft
acids and, ~ n d e e d there
, IS a linear correlat~onbetween
any two of logo, for [AuX2]-, [AgX,]- and [CuX,]-, where
o2 are the s t a b h t y constants for different ligands X. Again,
gold(1) discrimmates more than copper(1) or silver(1) between
the ligands. T h ~ is,s of course, tn agreement with the general
predictmn that largr metal tons In low oxidation states w ~ l l
have the greatest "class In" o r soft character.
Stabll~tyconstants for gold(1) 111 aqueous solution are
difficult to obtilin duo to the tendrncy t o disproportionate,
and more. e ~ t c ~ n ~datat v o h a w h w n obtained [ 36, 371 for
ac.tton~trtlcs o l u l ~ o n shy s t ~ i d y ~ nthv
g qi1111br1a
Ph,PO iMt.,S K py S< AsI'h , < NII, < Pt'h, - MeNC
Again, the data show quite clearly that gold(1) is a "class b"
metal ion. This is confirmed by studying complexes of gold
with ambidentatc ligands, in which both gold(1) and gold(II1)
a l n ~ o s invariably
i b o l d t o the solter end of the ligarid [38].
* However, evidence that gold(II1) is a softer acid than gold(1) has been
presented recently [29 1.
Thus, complexes with NCO- ligand are N-bonded rather than
0-bonded, with NCS- they are S- rather than N-bonded, and
with thiosulphate or sulphite they are S- rather than 0-bonded.
In certain cases, thiocyanate complexes of gold(1) have been
shown to contain a small proportion of the N-bonded isomer
in equilibrium with the S-bonded form [39]. The amount of
this N-bonded form in the complexes LAuNCS increases with
the trans-effect of L, decreasing in the order L = P(OPh), >
PMe, > PPh, > AsPh, > S(CH,Ph),. This is an example of
anti-symbiosis, in which a soft ligand bound to a "class b"
metal destabilises the bond between the metal and another
soft ligand trans to itself. In all complexes studied the seleno-
cyanate ligand is Se-bonded in goid(1) complexes.
It should be realised that the stability constant for a complex
is not determined only by the metal-ligand bond strength.
Thus, the enthalpy of substitution of chloride by bromide in
[AuCl,]- in aqueous solution is -46 k J mol-', but, after con-
sideration of hydration effects, the estimated bond energy is
greater for the AuCl bond than for the AuBr bond [40].
THEORETICAL STUDIES O F BONDING IN GOLD COMPLEXES
Molecular orbital calculations using the SCCC-LCAO-MO
method have recently been published for some halide and
pseudohalide complexes of gold(1) and gold(III), and the
results are of considerable interest [41, 421.
For the halide complexes [AuX4]- the calculated 5d-orbital
energies for gold fall in the order d, 2 < d,,, d,, < d,, <
-,
d,z 2 in agreement with the predictions of simple crystal field
theory and with similar calculations on square-planar platinum(I1)i
and palladium(I1) complexes. For the corresponding gold(1)
halides [AuX,] - the 5d-orbital energies for gold follow thc
-,
sequence d,, , d, 2 2 < d,, , d,, < dZ2 again as expected from
crystal field theory. The electron configurations of A U ~ ' and
Au+ are of course 5d86s06p0 and 5d'06s06p0, respectively, but
the calculated orbital populations and charges on gold and
halogens in various complexes are given in Table 1.4.
TABLE 1.4
Orbital population and atomic charges in the complexes [AuX4 ]-and [AuX2] -
"y = c.lrctronic chargo on the Au o r X ion
The data show very clearly that there is considerable co-
valency in the metal-ligand bonds for both gold(1) and gold(II1)
complexes. Thus, the orbital populations indicate that the 6s
and 6 p orbitals of gold are engaged in bonding, and that the
charge on gold in the complexes is always less than +l.The
extent of the covalency, which is largely due to a-bonding,
increases as expected on passing from fluoride through t o
iodide complexes.
For linear gold(1) complexes the simple bonding schemes
suggest that the filled 5d orbitals will play no part in bonding,
and that a-bonding will use 6sp-hybrid orbitals on gold. In
agreement, the calculations show that 6s and 6p orbitals on
gold are strongly involved in bonding in [AuX,]-, but also
that the 5d-orbitals contribute significantly t o the gold-halide
(J-bonds. This is in accord with the ideas of Orgel on d s
mixing in linear gold(1) complexes, discussed earlier.
For square-planar gold(II1) complexes Valence Bond theory
predicts that gold(II1) will have the 5d"onfiguration and that
a-bonds will be formed using the four 5d,z .26s6pX6p,, hybrid
orbitals. Again, the calculations support this, so that the 6 p
orbital population is considerably greater in the gold(II1) than
in the gold(1) complexes, while the reverse is true for the 5d
orbital populations. Similar trends were observed in the thio-
cyanate and cyanide complexes.
THE Z'KANS-EFFECT AND TKANS-INFLUENCE t h e a-donor ability of t h e ligand. Thus, in linear gold(1) com-
plexes, for example, the gold atom is sp-hybridised so t h a t a
These two concepts are widely used In interpreting the bromide ligand in [AuBr,]- will overlap with a gold orbital
chemical properties of squaw plar~arplatinum(I1) complexes, having 50% S-character. Now, a strong a-donor ligand like
but have not been exploited similarly for iso-electronic gold(l11) AsPh, will have a particularly high demand for t h e s-orbital of
complexes. As we shall see below, however, the cunc.epts are gold in order t o give the strongest possible covalent bond. Thus,
potentially very useful and, as more structural and mechan~st~c. t h e gold orbital involved in bonding t o AsPh, in [AuBr(AsPh3)]
data are accumulated, zrr llktly t o br used morc frequently In
ratio.lalismg t h cht~m~r-a1
~ properties of both gold(1) and gold[ I l l )
T A B L E 1.5
iwmplexes.
I'he tsutzs-cfft~tis cldined ,L. tht. dbi,lty o f a hgand to Gold - -chlor~nc,a n d golti---brominv bond Icsngths in s o m e complexes
lab~lisethe llgand Irurrh to , t ~ . : f .m d h c . ~ ~ ito
c c l ~ r c ~~l'c~o i n l n g
!~gandst o this posl, icln For t~x,rrnplc.111 the cornple?i [,ZuC'I , Complex lri1ri5 11g,1nd
(PPh,)] tht. trutls c ~ f f t of~ t Ph ,P 1s q(1atr.r t hsn that o f Cl , so ( ; o l d ( I l l ) c~ornpl(~\c\
that we expect the c.hloridth [ran\ to Irii>hc~r~j.l~,hosph~nc. to h [Ph4i\sj I i\uCl4I ('I
more labile than the otntv two chiorltlr ligands tlmct., thls [AuC'l {(PPh \ ) l ('I
c h l o r ~ d eis c)xpectc~Ito he displacwl prcfcrcmtially and the I'Ptl (

incomlng hgand will bc dirertctl to the stcreochem~calposition c [ A u C : I ( C ~ F ~ ) ~ ( P(1PI ~ I ('85

c I\ [AuC12(Ph)(SPr2)I SPr,
trans t o trl~,htnylphosphinc.'I'hc. trans-cffcc-t 1s thus a klnc>t~c
PI1
concept, and we shall return t o discwss ~t m o w fully In r h a p t t ~ r
9.
'The trans-influence is defmed a5 the ability of a ligand t o
weaken the hond between the meltal and thc ligand tram to
Itself, In the ground state of the rnolrcwle. 'Thus, in contrast
t o t h e truns-effect, it is a thermodynam~c* cwncept. The trarls-
influence of a llgand is dclducwd by measuring such parameters
ds t h e metal Iigand hond lengths by X-ray diffraction or t h r
metal-ligand stretching force constants by analysls of the
vibrational spectra (;old--chlorine and gold--bromine bond
lengths for some selected complexes of gold(1) and gold(II1) will have more than 50% S-character, leaving the d o n o r orbital
are presented in 'Table 1.5. of t h e trans-ligand, Br , t o overlap with an orbital having more
From t h e gold-chlorine bond lengths for the square planar than 50% p-character. Since t h e p-orbitals are more diffuse
gold(II1) c o m p l e x e ~it, is poss~blet o deduce t h r trans-influence than the S-orbital and, hence, overlap is less effective, t h e
-
serles: Ph C,F, > PPh, > SPr, -C1 . Prom the gold-brom~ne resultant Au-Br bond is weaker and more ionic in [AuBr(AsPh,)]
bond lengths for the lmear gold(1) complexes, it follows that than in [AuBr,]-. The spectroscopic properties of gold(1) and
the trans-influence of AsPh, > Br-. gold(II1) complexes can often be rationalised using t h e trans-
I t is thought t h a t the trans-influence of a llgand is largely influence concept and we shall return t o t h e topic in Chapter
d e t e r m i n d by t h e electronegativlty of the donor atom o r by 10.
 35 A. D. t i o o l s b v a n d D. 1'. Sawyer. Anul. C11c.m.. 4 0 ( 1 9 6 8 ) 1 9 7 8 .
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( 1 9 7 3 ) 2405.
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2 W. S. F v f c dtid K. W. I i r n l r v . Illr~c,r S C I . I.rr L... 5 (11373) 2 9 5 . R8 .I. L. B u r m r ~ s t t ~ a nr d N . J. D e S t e f a n o . Inorg. Chem.. 10 ( 1 9 7 1 ) 9 9 8 .
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3 P:. D. K < ~ r o b u s h k t n d 4. , S. C ' h t , r ~ ~ b d<kI I I ~(; XIIII,.~,\,l l ~ l : r - o l ~ l.'{ ~ ~ ~ l ~ ~ ~ ~ ~ ~ ~ , 4 0 B. I. P e s h c h r v ~ l s k ~ dn i d V. I. Belcvantsev. % h Nfwrg. Khim.. 1 4 ( 1 9 6 9 ) 2 3 9 3 .
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4 5 ( 1 9 7 6 ) 535. 3 1 4 .
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~, l ' t ~ t > l ~ s t ~I ,t o~nr i~i t~>, ~ 1~9. 7 - L 4 2 II. Z w a n l ~ g r r .l. . t t c ~ n h o l da n d b:. I I o v r r . %. t ' h r ~ m . . 1 4 ( 1 9 7 4 ) 4 8 9 : 1 5 ( 1 9 7 4 )
5 ,J P. R ~ l r \ III . .l. P K11k.y dnd <; S h i t ' r < ) ~(l*;d,.). \ ( ' I z ~ ~ I I I IO~ ~ ~ ~~I ~~ I Z I ~ ~ Vol ~ U ~:{,~ I ! I / I \ . 69.
4rarlcn11c Press. I . ~ , n ( l ~ r n2.n d t,d 19 7 b. ('h 10.. 4'3 P. G. .Jonrs, .J. . l . C;ur .incl C;. M. S h r l d r ~ r k .Acta Crvslollour., Scct. B . , 3 1
6 A . I. K v a b t n ~ n ,A S. K i ~ i n d n < , \S. t i h , ~ t a n r o v,tnd K t i h , i m ~ d o ~ . x( :. c ~ ~ ~ k / l l l r l r ~ ~ . ( 1 9 7 5 ) 2687.
(1974) 1 5 8 9 4 G. Bandoll. I). 4 . C'lvtncmtr. i;. M ; ~ r d n g o n ia n d L. Cattalini, J t'hrzm. S r ~ c . ,
7 B. I. Pt,shchev~tskii,(; N . Ano5hrn r n d A h1 I.:rt,nl)urc. 1 1 ~ ~ 1 \~k1u ( l t \ c l t ~ l ~ I ) u l t ( ~ tl'rurt.,.
~ (I!j7.3) 881;.
,S,SSR, l ( j 2 (l:lt;:>) 0 1 5 K:?> r j 1 i . , , , , 4 11 ,,,,, O 1 : t ~ ~ l ~( l~' i,7l l~l l l i l l ' / : , ,!I \ h \ f , 4 5 R . W . Baker ;rnd P. .I. I'.iul~ng, .J ( ' h ~ n t .S o c . , ( ' h ~ r n .Cornmurr ( 1 9 6 9 ) 7 4 5 .
7 5 (1971) 67332. .If; M. M c P ; l r t l ~ n.ind A . . l . Mdrkwrll. J . O r B ~ : n ~ , m c ~C'hc.rn.. l 5 7 ( 1 9 7 3 ) C25.
8 M. I. H r ~ t t a n Arn , S ~ . .I ti2 (197.1) 402 17 N. C'. f L w n / ~ x c r W. ~ K. Fknrit~tL< ~ n 1) d hl. .S<!t><broff% : l c , l u ( ' r v . s ~ d l ~ .%,cl
~ ~ r , B.,
9 R. J. :\damson ( E d . ) , ( ; < ) I d 11, I o l I ~ ~ r yI ,v) \c>t!llt \ ! , ~ , Y TL.h ~ i t n b c ~, >t l %lint'- R32 (197ti) 9 6 2 .
S < > u t h, \ f r ~ c ~. rI ,s ~ t i a i ~ ~ ~ ~1~9\7\ 3~ u r g l 8 .l. .l G u v . P. G. .lonc,s, M . ,l. M'IN 'ind C;. M. S h t ~ l , l r ~ c.J. k , I'h,,rrt .S<i<,, I l t ~ l l o n
l 0 .l K o r d ~ s .K A i ; ~ n ~ t , r ~a cn h d K , , l , Svvst-, .l I'/i',m 1'111,s . lil ( l : ) 7 4 ) '>l 14. I'rans.. ( 1 9 7 7 ) 8 .
,J. I h ) r ~ ~ ) h uTIr,,
e , .Stt-u(~lu~-v.s 01 111~~ 1, ivrirt,r2/s~ LVII<.\, N t ~ w Y
, < ) r k , l 9 7 l .l9 (;. .l. h r d ~ .KC(. 'l'?-01, ('llun I'<lvs /$,IS.X I ( 1 9 6 2 ) 3 0 7 .
I 1 ( a ) M. N . I / r y t ~ d n ~i;\ , h K h I ~ ~ 1 ~ 1 1 1 an(l k o ~ ,V. t 2. Krtlll~l\i.L11 , V ~ . o t . l i 1\111'f1 . 5 0 M. ( i . B. Drew ,in(J M. .l. I{Ic.<II, .J i'Ir,,m .Sot . l)ul1<111'l'rurrs., ( 1 9 7 3 ) 5 2 .
1 8 ( 1 9 7 3 ) R1 8 : f'lt~,rr~ .Ihalr.., 7 9 11:47:0 102!l!3 51 l'. 'S. B v u r s k t ~ n ~ 11., .l. ,A ~ % I ~ I ~ I L I .l. w . A ( ' r , % s,>nd .l. .l. Stc,gg<,r(l,~, III<,?-B( ' I ~ ~ ~ r r i . .
( b ) D. blclntosti ' ~ I I C I (>. A 0 / i 1 1 . l,,orc ~ ' I I , ~ l~ 5I .( I, 9 7 l i ) ZXfi!). It; ( 1 9 7 7 ) : > l . 7 ( 1 9 6 8 ) R05
H. H u b e r , l> M ~ ~ l n t o s~t i n C;d. S\. I > / I I I . I T I < , I (C .
' I I < , I I I l t; ( l ! l 7 7 ) 9 7 5 . 5 2 1%'.W. k'111stc.111. I I I I I I(. l l + , b t ~ \ o. . \ ( , / Ui ' ~ ~ \ ~ l u l l o. .S'-<
y r 1 l!.. H:Jl ( 1 9 7 5 ) fi24.
1 2 N . C. R d c n t ~ g e r .K. M. D ~ t t r l n < , r.tlld r .l. I< L>ovI(~.1,zor.C' i'111.n.. 1 3 (197.1) 8 0 5
l 3 P . L. bellon. h1 h l d ~ ~ d s w rdnd u 11. S ~ I I S < I I/I<I I. ( ,S<,#, :<!) (l!jli!J) l 7 3
1 4 J. C. M. 'T. F:~]ndhovf>ndnd C;. C. Vt.rschw,r-, .'.lcilcr. K(,.>. llu11., !) ( 1 9 7 1 ) I t i t 2
1 5 F'. Klanhcrg. E I,. Mut.ttt.rl~i~s and I.. .l i;uggenhcrg(.r, I r l o r ~ .('hcam 7 ( I 9 f i 8 ) .
2272.
1 6 H. S r h i n ~ d b d u ~ I ~r n dK. F r ; t n k ~ .i'11r)nl. 1{<,1,. 1 0 5 ( 1 9 7 2 ) 2!)85
1 7 R . I,. R i c h and H. 'Saubr. J . f'lr v,, C'hc~rn..5 8 ( 1 9 5 4 ) ti.
1 8 H. S ( ~ h r r t r d b ~ i u c. Ir. . K . h l , ~ n d l ,A . Fr'ink d n d (;. I l u t t n t ~ r t. ' h < . r r ~l3t.r.. 1 0 9 ( 1 3 7 6 )
466.
I 9 J. G . XI. \ , m Ken,. M. P A . VlW?r\ .tnd E : (Jr. Bt,t,r. ('1ii.111 1'11~s1,elI 2 8 .
(1974) 104.
2 0 4 . A . B r ? / u h c t i k o .ind H. I. Pt.cht.hevitskir. C J ~ < , ~/ r\ h~ r l r . . 56 ( 1 9 6 2 ) 20.1!4li.
.
2 1 W . 'L'. R o b ~ n s o nd n d E . S m n . J ('111~rrtS < , ( ., I)ullr,t~ I ' r o r ~ s ( 1 9 7 5 ) 7 2 6 .
2 2 V. F. D u c k w o r t h .rnd N . ('. S l e y h ~ ~ ~ j s Jttr,lg on, ( ' l ~ < ~ Xn ~(l!)fi9)., I lifil.
2 3 I. N. Bakulina a n d N . l. l o n o v . I l o l ~ lAl:(ld &ru1112 .S,sSll. l 5 5 (191; 1) 309.
2 4 E. Y . Z a n d b c r z . !\. (i t i d ~ n ~ ~ ,rnd n r v V . I P;11wb. %h 7',~1?11FL;.. 4.4 ( I 9 7 L ) til 7
2 5 R. D. H a n c o c k ,tnd N . P. F ~ n k c l s t r ~ Irzorg n. ,\'tlc.l ('1r"m 1.1,11.. 7 ( l l l 7 l ) -477.
2 6 R . S. N v h o l n ~ P , r o c ('h<,n~ S ~ J C ( I Y(i l ) 2 7 X
2 7 L. E. Orgel. J. C'hcm. Sot..( 1 9 5 8 ) 4 1 8 6 .
2 8 C. K . .Jdrgensrn a n d J. P o u r a d ~ e r J. ('hint. I'hys., 6 7 ( 1 9 7 0 ) 1 2 4
2 9 C. J . Hawkins. 0. M o e n s t e d a n d .I. Hjrrrum. A c l a C h c m S c u n d . . 2 4 ( 1 9 7 0 )
1 0 5 9 ; L. H. S k i b s t r d dnd J. B j e r r u n ~ A . e t a Chc,rn. S c u n d . Srpr A . 31 ( 1 9 7 7 )
155.
3 0 L. M. G e d a n s k v a n d L. G. Hepler. k'nyc'lhurd I n d T i ~ hIJull., 1 0 ( 1 9 6 9 ) 5.
31 N. P. F i n k e l s t r i n a n d H. D. H a n c o c k , (;old Hull.. 7 ( 1 9 7 1 ) 7 2 .
3 2 A. H a k a n s s o n a n d I,. J o h a n s s o n , C h e m Scr.. 7 ( 1 9 7 5 ) 2 0 1 .
33 V. P. Kazakov. A . I. Lapshin.and B. 1. P e s h c h e v ~ t s k i i ,%R. .Vr,r>r.p K h ~ m . ,9
(1964) 1299.
3 4 L. H. S k i b s t e d a n d J. Bjerrum, A r t a C h e m . S c n n d . . Scv A.. 2 8 ( 1 9 7 4 ) 7 6 4 .
CHAPTER 2 HALIDES O F GOLD

The known halides of gold, together with some thermo-

BINARY COMPOUNDS OF GOLD dynamic data 131, are listed in Table 2.1. It can be seen t h a t
only fluorine gives a gold(V) derivative, while iodine gives only

TABLE 2 1

Hn1ldt.s <,F gold and thr~rmodynammcdata a t 298 K for c r y s t a l l ~ n e

compobnds

Ljgk/, Allf*'/ AGJ

('ornr~c)und ('olour g cm kJmol l k.1 m01 '

The monomeric compounds AuFl and AuI) certamly exist in

the gas phase when gold is heated t o about l ZOO 'C: In an
atmosphere of hydrogen or dt.uterium, respectively. Deta~led
spectroscopic studies have been carried out on these compounds,
and as a result the bond d ~ s s o c i a t ~ oenergy
n a11d Au- H bond
d ~ s t a n c eare calculated t o be 310 k J mol-' and 152.5 pm,
respectively [ 2 ] .
'I'herc. 1s 110 cv~drnc.rfor thc c>x~stt.nc~ of AuF and c.st~matrd
thermodynamic. data ('Tablr 2 1)suggest that ~tw ~ l bt. l unstable
w ~ t hrespect t o dlsproport~onatlont o gold and AuF3.
AuF, was f ~ r s prepared
t 141 by h e a t ~ n gAuF,.BrF,, formed
by dissolut~onof gold In BrF,, a t 300 'C. The product formed
m this way is contaminated with bromine, and the pure com-
pound is best prepared by reactlon of either gold(II1) chloride
or gold powder with fluorine at high temperature 15, 61.
Gold(II1) fluorlde can be sublimed a t 300 "C' under vacuum
t o g v e bright golden-yellow needles. It decomposes a t 500 " C
t o gold and fluorme, and IS a powt.rful fluormating agent,
causlng b r n m w to burn I t forms the ,iddu<ts I u F , RrF,,
I u F , %.F, and N O [ ,ZuF, ]
AuF, is diamagnetic s h o w n g that gold( l11 1 has t h e usual
low s p ~ ndn cwnflgurat~c~n, and thc ( ompound has a unlyue
structure whic h I , illustr;h~d F i g :l 1 i t (.,in hr drscrlhtd
e r ~ d tgl rh t , h ~di i i , i i i t k ) c , i \ n i t I , tht* hai:~,btbing
da a f l ~ ~ o r i til~
rosc 11rlkmi \\lth M'~>;II\I>T f l i : r ~ r i l ~hridgt,.
f~
fr)rms strong bond5 to t ~ b otcrnl~n11 <incltw,vr, is bridging
b u t is associated by the presence of fluorine bridges. The
structure is n o t known with certainty but, from powder X-ray
photographs, a structure similar t o that of RuF, is suggested.
This is tetrameric with bent R u F R u bridges, each ruthenium
having approximately octahedral stereochemistry. AuF, is a
dark red solid which melts over the range 75-78 "C, and can
be sublimed under vacuum. It combines with oxygen and
fluorine t o reform [ 0 2] [AuF61, with XeF2 t o give
[ X e 2 F 3 ][AuF,] and with NOF t o give [NO] [AuF,].
Attempts have been made t o prepare gold(V1) fluoride,
which is expected t o be the most powerful oxidising agent of
F;ic h gold dtom the third transition serics mt.tal hexafluorides, h u t all attempts
(
have failed.

( b ) Chlorides of gold

Reactwn of chlorine with gold may p v e cither gold(1)

IJI
Flg. 2.1. The structure of A u F , . ( a ) Part of a helical chain, ( h ) t h e
ordmation a b o u t gold(I11).
fluorides t o g v e overall a square-planar arrangement of
fluorine atoms ahout t w h gold centre These square-planar
gold units are linked togethtlr by thr. bridgmg fluorines t o g v e
the helical-chain structure 'I'herc 1s then add~tionalweak cross-
linking in w h ~ c hthe terminal fluorines occupy positions above
and below the square-planar gold(lI1) centre of another chain,
t o g v e an approximately tetragonally d ~ s t o r t c doctahrdral
environment about each gold atom.
Gold(V) fluoride [7, 81 can be prepared by thermal de-
composition of either [ K ~ F ] + [ A u F ~o ]r of [ 0 2J S [ A u F 6 ] .
Gold(V) fluoride is diamagnetic so that gold(V) has t h e low
spin 5d6 electron configuration. It is certainly n o t a monomer,
chloride or gold(l1I) c h l o r ~ d edeprwd~ngon the rtactlon con-
ditions. A claim that Au('1, could hc formed has been disproved.
The thermodynamics of the gold chlorin(. s y s k m have
CO
been thoroughly studied ( 3 , 9, 101, and some of the more
important conclusions arc discussed here. At room tempera-
ture gold(1) chloride is metastable, and very slowly dispropor-
tionatcs t o gold and gold(ll1) chlor~de,Au2C1, At a chlorine
pressure of one atmosphere, Au2C16 exists as t h e only species
in both solid ( S ) and gaseous ( g ) phases a t temperatures below
254 OC. At temperatures hctwecn 254 "C and 282 "C, AuCl(s)
rxlsts together with Au,Cl,(g), while above 282 "C Au(s),
Au2Cl,(g) and Au2Cl,(g) coexlst. Thus Au2C1, can b e pre-
pared by reaction of gold with chlorine a t temperatures below
254 " C . Typically a rapid flow of c h l o r ~ n egas is passed over
gold a t 240 'C, when Au2C1, is formed and sublimes t o g v e
red crystals on the cooler parts of the tube. Alternatively, the
reaction can be carried o u t a t 250 " C in a salt bath [l11.
Large crystals of the yellowish-white AuCl can be prepared by
vapour transport of Au,Cl,(g) in an atmosphere of chlorine.
Thus Au,Cl,(s) contamed a t one end of a tube is heated t o
247 'C, and is deposited as AuCl(s) a t the other end which is

Fig. 2.2. The s t r u c t u r e of AuCl
and gold(II1) sprcies including [AuCI,(OII, ) ] is very rapid in
water, and AuC1 must he stored in a desiccator t o minimise
this mode of decomposition. In the gas phase goldil) chloride
exists as the dimer Au,CI2, which may have a vyclic structure,
and for which the enthalpy of dissociation t o monomt>ric
AuCl is 68 k J mol '
[l31 .
The most typical reaction of AuC1 is t o form complexes of
the type LAuCl, for which the ligand L may he ammonia,
pyridine, a trialkylphosphine, a dialkylsulphide, carbon mon-
oxide, an alkene and many others. These, and complexes
derived by addition of more than one equivalent of t h e ligand
L, will b e discussed in Chapter 3. AuCl dissolves in concentrated
sodium chloride solution t o give Na[AuCl, ] but the [ AuC1, ]
ion is itself decomposed by water t o give Au and [AuCl,] .
Gold(II1) chloride has t h e dimeric chlorine bridged structure
shown in Fig. 2.3, in which each gold atom has square-planar
stereochemistry .
Fig. 2.3. The s t r u c t u r e of Au2C16
'fhesr reactions do not take place, however, if the aromatic
compound contains a suhstitucnt which can co-ordinate t o
gold. Thus bc?nzonitrile and a z o b ~ n z e n tform
~ simple nitrogen-.
donor complexrs of the type [ IAuC:l, ] 1191.
A particularly stable graphite insertion compound of
conlposition C , AuCI, is formed by direct reaction of
graphite with [iZu,Cl,]. The stability is due t o the short inter-
planar distance of 680 pm, n o d o u b t made possible by t h e
planar structure of [Au,CI,]. This dimeric structure of
[Au, Cl,] persists in the gas phase [g, 141, and the enthalpy
of dissociation t o monomeric [AuCl,] is estimated t o b e
77 kJ mol-' .
Many claims for the formation of t h e compound "AuC12"
have been proved t o be false, b u t a black compound of this
empirical formula is formed by reaction of gold(II1) chloride
in thionyl chloride v i t h a deficiency of carbon monoxide.
The reaction gives [Au(CO)Cl] in the first stage and this
reacts with excess of [Au2C1,1 as follows:
[Au(CO)Cl] + (Au,Cl,) 4 + Au, (CO)Cl,
The product XuClz is diamagnetic and so is most 11kely a
mixed gold(1) gold(II1) species; this is confirmed by the
structure determination [ 1 9 b ] which shows the p r t w n c c of
cyclic [ilu4C18] nlolecules with linear gold/I) and sy uare
planar gold(II1) centres as shown in Fig 2 3
Fig. 2 . 4 Thc s t r u c t u r e ot r\u4Clh
( c ) Bronzidcs and iodides of' gold
Gold(lI1) bromidc is formed hy thc exothermic reaction of
gold powder with liquid bromine. It forms dark red-brown
crystals. The structure is dimeric like that of [Au,Cl,] though
the full crystal structure has n o t been completed (131. Its
chemic.al properties also resemble thosc of [Au,Cl, 1. Thus ~t
reacts with nitrogen donor llgands, L, t o g v e complexes
[LAuBr, 1 and IS reduced by tertiary phosph1nc.s and arsincs
and by dlalkylsulphides to g v e conlplexes [LAuBr] . On heat-
Ing t o a b o u t 2 0 0 "C, [Au,Br,] decompostls t o bromine and
AuBr. Again like the corresponding chloride, this is moisture
sensitive, decomposmg t o gold and gold(II1) species, and forms
complexes [LAuBr] with many ligands L and the complex Ion
[AuBr,] with bromide. AuBr decomposes t o t h e elements o n
bemg heated above 250 "C.
Several claims have been made t h a t gold(II1) iodide can be
prepared from solutions of gold(II1) complexes containing
iodide ions. However, many gold(II1) complexes readily
oxidise iodide t o iodine, and it now seems likely t h a t t h e
isolated compounds with empirical formula Au13 are actually
compounds of gold(1) with 1, rather than gold(ll1) iodide
[ 2 0 ] . The compound AuI, readily eliminates iodine t o give
gold(1) iodide, which may be obtained directly by reaction
of iodide with aqueous solutions of Ii[AuC14] or, slowly, by
direct reaction of gold with iodine a t elevated temperature.
It forms yellow crystals which are much more stable t o water
than AuC1, probably due t o its much lower solubility [ 2 1 ] .
It dissolves in water in the presence of iodide ions t o give
[ A u I , ] , and in i o d i d e iotlinc solutions t o give mixtures of
[ A u I z ] , a n d [Aul, 1 .
The structurt. of AuI is likv that of AuC1. Each gold is
lint.arly co-ordinatid t,o two iodine atoms a t a distance of
262 pm with four more iodinrs further away at 3 0 8 pm [ 2 2 ] .
Gold(1) cyanide is r ~ a d i l yformed by heating K[Au(CN), 1
with hydrochloric acid. It forms yellow crystals, which have
a polymeric structure with linear A u C N A u C N chains. It is
-
insoluble in w a k r b u t dissolves readily in the presence of
cyanide as the romplcx ion ( A u ( C N ) , ] . This reaction has
bcen invoked as the final step in t h dissolution
~ of gold by
cyanide in the prcwncc o f oxygen (231 .
Anhydrous gold(lI1) cyanide is n o t known, probably due
t o its inability t o dimt>risclike thc gold(l11) halides, b u t the
complex A U ( C N ) .~3EI,O can be prepared b y dehydration of
solutions of kI[Au(CN), 1 . Its structure is n o t known, b u t i t
decomposes readily t o gold(1) cyanide on being heated.
An alternative route t o gold(1) cyanide is b y heating
dialkylgold(Il1) cyanides, and this method has also been used
t o prepare gold(1) thiocyanate [ 2 4 1. Thus, heating
[(Et, AuSCN), 1 in xylene a t 1 2 5 "C gives AuSCN as an
insoluble colourless powder, which decomposes t o gold a t
1 4 0 "C. AuSCN dissolves in water or alcohol in the presence
of thiocyanate Ions t o give [Au(SCNJ21 , which d e ~ o n ~ p o s ~ s
rather rapidly in water. The potassium salt K [ A u ( S C N ) ?1 can
be obtained from ethanol, however.
OXIDES A N D HYDROXIDES O F GOLD
Gold(l1I) h y d r o x ~ d eAu(OH), 1s fornlrd hy a d d i t ~ o no f
sodium hyrirolilde t o solutions contamliig [AuC'l, j 'I'his
hydroxtde c m be dehydrated to gtvt3 flrst . Z u ( 0 ) 0 Hand then
A u 2 0 3 .r!u2O3 decomposes t o gold a i d oxygen above 1 6 0 "C'
The most recent dt.terrnlnatlon g~\c.s 1H,"( . 2 u , O , ) = 1 3 O +
2 3 k J mcrl ' , and , \ U 1 u z0,acts 3s a truc rnc~almt>tal o x d r
riec r r c d t ~byhtt~rnM ~ t h7 1 .X 125. 26 I
(;old( l [ lI i ~ b d r ~ \ l d~ <t ~' c LSi ~ \ \ ~ t hiIc3r( I I I U ~ I <<I< fjf.111~
heated in 3 wild t u k ,it 150 - ( ' for 2 wt.t.k< to givc3rml
transparmt crystals of ZuO('1 'I'hf. gold( l l l ) o x ~ c l rc~h l c w d ~ ~
decompows to the elcments at 290 "C' 1271. ~ L I ( O ~isI ) ,
gcncraily known as aurtc acxt s1nc.t. 11 I)c,havc.sas a n c ~ ' i I \ .IL i t i
Thus ~t dlssolves rmdily in K011 solution to g i v ~aftrhr t w p o r -
ation K , I u O , t'3fi20 w h ~ probat)ly h ~ w n t a i n sthc [ , \ u ( O l l ) , j
Ion. Neutraiisatlon of buc.h w l u t ~ o n ,leads to rr3prcc~ p i l a t l o n
of gold(lI1) h y d r o x ~ d c Although the hydroxide is solublc t o
some extent in s u l p h u r ~ cor n l t r ~ cacld, t h c 1s ~ no midence
for formatton of the ayuogold(ll1) ion In the s o l u t ~ o n s'I'herv
1s e v ~ d e n c ethat the spccles [f12.CuO, ] , [ I I A L ~, O l 2 and
[ AuO 1 uc formed on treating ,Zu(OH), with ~ncrrasingly
concentrated hytiroxlde solutions, h u t thc structures of thcsc
~ o n are
s n o t known 1281.
Reports of the cxistencar~o f gold(l) oxide and gold(1)
hydroxide are now regarded w ~ t hsceptictsm, b u t the o x ~ d a t i o n
of CsAu with oxygen at 400 "C has been shown t o gIve the
aurate(1) derivative CsAuO 129 1 .
SUI.PHIDES, SELENIDES AND TELLIJRIDES O F GOLD
Gold does n o t react directly wlth sulphur, b u t the com-
pounds Au,S and Au, S, can be prepared. ( h l d ( 1 ) sulphide IS
formed b y reaction of [Au(CN), 1- with 1-1,s.It is a black-
brown powder which is only very slightly soluble 111 water (301
(K,,, = [ A ~ f l[*s 2 '1 4 X 10-''%t 25 " V ) but which ~ I S S O ~ V E S
in cyanide or polysulphide s o l u t ~ o n sThe. standard Gibbs free
energy of formation A G f - 1s +29 kJ mol-I . In t h e gas phase
a t high temperature Au,S molecules apparently exist [31].
Gold(1II) sulphlde can be prepared b y reaction of H,S wlth
[Au,Cl,] In anhydrous ether a t low temperature. Attempts
t o prepare ~ttn aqueous solution lead t o reduction t o metallic
gold. The black powder decomposes t o t h e elements on being
heated t o 200 "C. lt dissolves with decomposition t o
[lZu(('N)2 1 in cyanide solution.
Two selenides of gold are known, AuSe and Au,Se3. There
x e two crystallme forms of AuSe, both of whlch form mono-
i
r
c lmic crystal?. The 0 form of AuSe contains gold in t w o forms,
onc w ~ t hh n t w co-ordinat~ont o t w o selenium atoms and t h e
other with square-planar co-ordlnatlon t o four selenium
atoms It 15, therefore, hest represented as Au(I)Au(III)Se,.
Gold rcac ts directly wlth tt~llunumt o glve AuTe,, whlch
also occurs In the rn~nc~rals calaverltr. and sylvanlk. The
crystals c o n t a n linear TrAuTe units. The standard enthalpy
of formatlon 41ir" 1s ( 1 8 . 6 4 3 ) k J mol ' 1331. In addition
.Zu,Tc, occurs in tht* rnlnr.ra1 m o n t b r a y ~ t cand a c-,npound
,,
of composition Au'l'e, is formed by reduction of solutions
contrunlng gold(II1) and tellur~um(IV)with hydrazine [ 3 4 1.
In addition t o thr, blriary selenldcs and tellurldes, the mixed
compounds AuBrSe, LZUI'I'~, AuClTe,, AuRrTc, and AulTe,
are known Typcally, A u l T t ~ ,1s prcymrd by reaction of
elemental gold and tellurium with h y d r i o d ~ cacid In a sealed
tubr a t a temperature of 450 "C, the mixture then bring cooled
slowly t o 1 5 0 "(' over a period of ten days [35, 361. The
compounds AuXrre2 all exhibit metalhc. conductivity, and t h e
structures have gold co-orclmated t o four tellurium atoms 137 1.
The structure of AuRrSe contains gold in syuare-planar co-
o r d ~ n a t l o nwlth some gold atoms co-ord~natedt o f o u r selenium
atoms and some t o two brom~nr.and t w o selenium atoms [38].
GOLD(II1) FLIJOKOSULPHATE AND NITRATE
Reaction of gold with bromine(1) fluorosulphate a t 65 "C
gives a complex A u ( S 0 3 F ) , . 213rS03 F which loses BrS0,F on
being heated under vacuum t o give Au(SO,F),. This is a bright
orange-yellow solid which melts at 94 "C. Its structure is n o t
known but lt appears to be polymeric wlth brldging fluoro-
sulphate groups [39]
Dissolut~onof A u 2 0 3 I n concentrated n i t r ~ cacid does not
g v e anhydrous gold(II1) nltrate but t h e complex acid
H [ A u ( N 0 3 J 4 ]. 3 H 2 0 . It has been cla~medthat r e a c t i o n of
this product with N 2 0 , followed h y heating of the product
under vacuum gves a golden-yellow suhhmate of Au(NO,),
at 80 "Cl4 x 10 ' Torr. The yield was very low and the
characterisation r e l i e d e n t ~ r e l yon analysis for gold [40J. The
claim must therefore be considered doubtful though cwmplex
nitratoaurates(III), LI'[Xu(NO , l 4 l , arc>w e l l c.haractrr~scd
[411.
NITRIDES AND OTHER (;ROllP V DERIVATIVES
N o simple gold nitrides are k n o w n h u t there was great
interest in the Middle Ages in an explosive substanw called
fulminating gold. This is formed by reaction of Au,O, with
aqueous ammonia or ammonium salts, by reaction of a
gold(II1) salt and an ammonium salt with base and by several
other routes. It has been variously formulated as AuN . NH3 .
13 H2 0, Au(NH)NH2 or A u 2 0 3 . 4Nf13 and probably several
different mixtures of compounds may he formed depending
on the preparative route. All cletonatcl to give gold, nitrogen,
ammonia and water.
The compounds Au,P, ( A H T -~-97.5or 48.5 k J m o l - l ) -
and AuSb, ( A t i f " - 13.1 k J mol-' ) can he prepared by
direct combination of t h e elements at high temperature 1421.
A u S b ? has the electrical properties of a metal [ 4 2 ] , and has
the cubic fluorite structure, the shortest A u S b and Sh-Sh
distances being 276 and 286 pm, respectively [ 4 3 ] .
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602.
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478.
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Uokl. Ahad ,Vaul; SSSH. 2 2 9 ( 1 9 7 6 ) 8 8 4 .
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4 5 (1976) 261.
10 E M . W . .lansscn. J . C . W. Folmer a n d G . A. W~egers,J. Less-Common Mrt.,
3 8 (1974) 71
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17 K . S. Ltddlc a n d C . Parkin. .l. Chcm. S o c , Chrnl. Comrn ( 1 9 7 2 ) 26.
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3 4 F . H. Hnwie a n d C . K. Veale. J Inorg Nucl. Chcm.. 28 ( 1 9 6 6 ) 1 1 4 9 .
3 5 A. Kabcnau a n d H . Kau. Inory. Synlh.. 1 4 ( 1 9 7 3 ) 1 6 0 .
3 6 A . Kabrnau. H. Kau and G. Kosenstein. A n g c u ~ .Chem. Int. 8:d. Enp.. 8 ( 1 9 6 9 )
145.
37 H. M. Haendler. D. Mootz. A. Rabenau a n d G . Rosenstein. J. Solid S t a t e
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Chcm 1 0 ( 1 9 7 4 ) 1 7 5 .
3 8 D. M o o t / . A. Kabenau. H. Wundcrlich a n d G . Rosenstein. J. Solid S t a t e Chem.,
6 (1973) 583.
39 W. M. J o h n s o n . R. Dev a n d G . H. Cady. Inorg. Chem.. 1 1 ( 1 9 7 2 ) 2260.
 CHAPTER 3
40 B. 0. Field and C . J. H a r d y , J . C h e m . Soc., ( 1 9 6 4 ) 4428.
41 C . C . Addison, G . S . R r o w n l e e and N . Logan. J . C h e m S o c , D a l t o n 'I'rans..
(1972) 1440.
4 2 W , D. Johnston. R . C . Miller and D. H. Damon. J I,t%s Common .11c2t.. 8
( 1 9 6 5 ) 272; C. E . Myers. T. J . Conti and N. F. Mar1ey.J. 1 . t . s ~ C o m m o n 2 W ~ z t , GOLD(1) COMPLEXES
48 ( 1 9 7 6 ) 213.
43 S. Furuseth. K . Selte and A . K l ~ k s h u s ,A c t a C h f m . S c a n d . 19 ( 1 9 6 5 ) 735.

In this c h a p k r the complext>sof gold([) are discussed

accord~ngt o the nature of the donor atom(s) of the ligand(s)
complexed t o gold. We shall examine complexes with group
I V , V, V1 and V11 donors in that sequence. Many of the group
TV donor complexes wlll h e discussed in subsequent chapters
on organogold complexes and on compounds with gold-metal
bonds, and hence only the carbonyl, cyanide and alkyl and
aryl isocyan~dec o m p l ~ x e sare considered here.

CARBONYL COMPLEXES [ I ]

The only well-characterised compound is [AuCl(CO)].

This was or~ginallyprepared by treatment of CO with solid
AuCl a t 9 0 'C. The carbonyl complex is a white solid which
sublimes in a stream of CO, b u t which dissociates back t o
AuCl and CO on being heated under vacuum. It can be pre-
pared more easily by bubbling CO through a suspension of
AuCl in benzene, in which solvent the product [AuCl(CO)] is
soluble, or by bubbling CO through a solution of [AuzCl,] in
tetrachloroethylene a t 1 2 0 'C. In the latter case phosgene is
formed [2].
[Au, Cl,] + 4 C 0 + 2[AuCI(CO)l + 2COC1,
A particularly convenient preparative route involves dehydra-
tion of the readily available tetrachloroauric(I1I) acid,
H[AuCl,] . 3 H 2 0 , with thionyl chloride t o give [Auz Cl6 ] ,
which is treated in situ with carbon monoxide t o give
[AuCl(CO)] and phosgene [ 3 ] . Anhydrous conditions are
necessary for the preparation since decomposition t o gold and
CO occurs very readily on reaction with water. Even moist air
or alcohol decomposes [AuCl(CO)] in this way.
CHAPTER 10 TABLE 10.1

Infrared a n d Kaman spectra of ions [ A u X 2 1

SPECTROSCOPIC STUDIES OF GOLD COMPLEXES

Most published papt>rson gold compounds now contam

spectroscopic data, most commonly from t h e infrared and
r1.rn.r. spectra. It would 1~ ~nappropriatrt o attempt t o give
a c u m ~ ) r t ~ l i c ~J ~~YsYi JvL I I o
~ ~f such sptSc.tra,and o l ~ l yvnough
(lata to show the klntl o f ~ t i f ~ ~ r r n aatbi o~ln~ strr~cturc
t and
h o n d ~ n gin g o l d ~~)m[)lc.;t)s which can hr. o b t a ~ n c dfrom
spwtroseoplc studltls w ~ l bc. l given here.

S t u d ~ e of
s g o l d l i g a n d stretching and other vibratmns by
mfrarcyi and Rarnan sprctroscopy can 3 1t.1~1uscful mformation
about the metal-ligand bond strength and t h e d e ~ ~ of e eco-
valency in the metal-ligand bond. 'I'he metal--1igand stretch-
mg frcyuency is dctermmrd by t h c masses of the metal and
ligand, by the stretching force constant whlch is related t o t h e
strength of the metal-hgand bond, and by couplmg o f this
vibrat~onwith other moltwdar vibrational modes belonging
t o thc same symmetry species. Idcally thereforcl, when com-
parmg metal ligand bond strengths t h e stretching force
constants should be calculated b u t this 1s difficult except for S t r t ~ t c h i n gforce, constants, l: / N m l, f o r s o m e linear molcru lw and ions
the most symmetrical molecules. We shall discuss such mole-
cules first.
-
(a) Linear molecules [A u X ,

There are three normal modes of vibration for these mole-

cules, namely t h e symmetric stretching vibration (v,, symmetry
C,'), the bending vibration (v,, symmetry nu)
and t h e asym-
metric stretching vibration (v,, symmetry C,'). v, is Raman
uncertainty of the assignments, but some trends become appar-
ent. Thus, there is a remarkable change by a factor of two in
the energies of the d-d bands between [AuCl,]- and [ Au14]-,
and the bands are all at lower e n e r g ~than ~ for t h e correspond-
ing [ p t x 4 j 2 -ions. This latter observation is exceptional t o
t,he general rule that increase in oxidation state leads t o higher
ligand-field splittings. It is suggested. that the u *-orbital
5d,2 ,.2 has more pure metal character for complexes of
Au3+than for p t 2 + ,but that the 5d,, level is more strongly
destabilised by interaction with the ligand n-orbitals for
A U ~ +than for R*+.The result is that the separation 5d,,. -+

5d,2 ,: is less for gold(Tf1)comploxrs than for platinum(I1)

comp1exr.s [73, 761. The very low separation in [ A L & - is
due t o w r y strong ligand-to-metal T-bonding in this complex.
Anothcr way of looking a t this is to say that the orbital 2h,,
(5d,, ) has consitlrrabie ligand character, and hcncr that t h e
transition 20,,(5d, ,,) -t 30 ,,(5d, L ,.2 ) has considerable ligand-
to-metal charge-transfer character and its energy takes on the
character of such a transition, decreasing sharply for the larger
halidc ions.
As well as the gold(II1) complexes discussed above, elec-
tronic spectra have been discussed for [Au(N,),]- [ 8 1 ] ,
[ A ~ ( N F I , ) , ] "[ 7 3 ] , [ A u ( C N ) , ] [ 7 3 ] and for several other
m i n e complexes of gold(I11) [79, 80, 821. It has also been
noted that the ligand-to-metal charge-transfer transitions in
organogold halides (R,AuIir), and [R,AuBr(NH,)] are at much
higher energies than in IAuBr,] , and the result is ascribed t o
the strong destabilisation of thc c;*-orbital 5d,z ,z on gold
by the strong U-donoralky l groups R 1831.
Although the u.v. spectrum of [Au(CN),]- is clear up t o
50,000 cm-', the spectrum of [Au(CN),]- contains many
bands below this energy. These bands are due t o metal-to-
ligand charge-transfer transitions, which are, as expected, a t
lower energy for the gold(1) than for gold(II1). A simplified
molecular orbital energy level diagram for [ Au(CN ), 1- is
shown in Fig. 10.4, and detailed analysis of the U.V.spectrum
of [Au(CN),]- confirms that the order of d-orbitals is 5dzz 2
5d,,, 5dxz- - , 2 > 5dXz,5d,,, taking the z-axis as the molecular
axls. Since t h r 5d,, and M, 2 , L arc. non-bond~ng,~t1s clear
that 5dy2 lssl~ghtlytlestah~lwtlt)y tr-l)ond~ng, and that 5d,,
and 5d, are slightly stabd~scdt)y ~ - t ) o n c l ~ tnog vacant T*-
orbitals of t h e cyanidc l~gands.tlowovcr the total splitting
of the 5d I r v t ~ is l ~(.st~matcdto t)t. no Inore than 5000 cm l,
mdicating t h a t thc ten 5d-clc~h-ons are cwcnt~allycore
electrons and arc ~nvolvedonly weakly In t~onding.'rhclre is
reasonable agreement h t w c ~ nthc o b s r r v f d and calculated
t r a n s i t ~ o nenergies, lending support t o those conclusions
[74, 841 . T h e U.V.spclctra of [ A u X , ] - , X = h a l ~ d e have
, not
hccn reported, hut are t1xpc~ctcdt o c o n t a ~ nonly very high
mcrgy bands, s~ncr.d cl transitwns are not possible for gold(I),
and Iigand-to-metal charge.-transfer trans~tionsare expected
to bt. a t high c3nergy for this low o x ~ d a t ~ ostate
n of gold.

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4 9 F . C o l e t t a , R . E t t o r e a n d A. G a m b a r o , Inorg. Nucl. C h r m . Lctt., 8 ( 1 9 7 2 ) 6 6 7 . CHAPTER l1
5 0 H , S c h m i d b a u r , H. F . Klein a n d A. S h i o t a n ~ ,C h e m . B e r . , 1 0 4 ( 1 9 7 1 ) 2 8 3 1 .
5 1 G . E. Glass, W . B. S c h w a b a c h e r a n d H. S. Tobias. Iflorp. C h e m . , 7 ( 1 9 6 8 )
2471.
5 2 D. I. Nichols. d. Chum. S o c . A , ( 1 9 7 0 ) 1 2 1 6 . ANALYSIS AND APPLICATIONS O F GOLD COMPLEXES
5 3 L. G . Vaughari a n d W . A. S h r p p a r d . J An1 ('hidm. S o <c . 91 ( 1 9 6 9 ) 6 1 5 1 :
J. Organornet. Chpnt.. 2 2 ( 1 9 7 0 ) 7 3 9 .
5 4 M. 0 . F a l t c n s dnd I). A . S h u l e y , .l. C'hcrli. /'tl\'.s.. 5 3 ( 1 9 7 0 ) 3 2 4 9 .
5 5 1%. D. B d r t u n l k . W . Potrr.1. K 1.. Mosshaucr and 0 . Kaindl. %. Phgs., 2 4 0
(1 970) 1.
5 6 J . S . C h n r l t o n dn<l 1). I. N ~ c l l o l s J. . Ctlr2rrl. S o c . A . (1!)70) 1 4 8 4 .
5 7 H. Prosser. C;. Worlrnan. K. Svasst'n m d W . B. Hol/apfCL, % Phvs. 13. 24
ANALYTICAL METHODS FOR GOLD [l-3 1
(1976) 7.
58 1, P f r ~ f f c r .I<. S. Raghdvan, C'. P. Llrhterru.ilnt,r dnil K . W . Wc.st. I'hys. HPII.
IA~ll...30 ( l 9 7 , 3 ) fi.35
Many analyt~calproced~lresfor gold determmation rely on
59 .l. ,\ J. J,ir\15, A . . J I ) ~ I I I W I I .III(I l<. .l I ' L I ( I I I ~ ~ I ,l. ~ ~(:h<,m.
I ~ I ~ L Sot
, , ('III~J~. gold bemg present as [AuCl, j . Gold as the pure metal, as a
('ornrrt~trr , ( 1 9 7 3 ) :j7:i. ,\. . l o h r ~ ~ o1'~11i 1) . 'I'/?,TI.\ ~ l n ~ v t ~ r sol ft vl , ~ \ , ~ ~ r ~ ~ o , ~ l .
l !4 7 ,5
constituent of an ore, or I n many complexes can r e a d ~ l ybe
S i O P c;. . ~ I I I I < ,4 S. !vlad(lock. XI. .l X L I Y~ ~I I A ~ .I b'. WIIIIAIIIS, !\l)strarL o f converted to the requ~redtetrachloroauratc~(II1)by dmolution
lfi1/1 AI,,clir~#,. A I ~ , , ~ S /~) i~. w I I~It .~%~~~(;IYIIIII.
~ o ! ~ ~ ' ~ I I I ' P ~ S 1I, ~1 1Y~ f ~ r p o 1
o9l ,7 6 .
(;l G K a ~ n d l .K 1 , w r ~a n d N . BartIctL..I ('/IPI?I I'hys. 5:) ( 1 ! l 7 2 ) 5 0 5 0 .
in aqua ryqa. N ~ t r ~ a cc ~ dand o x ~ d e sof n ~ t r o g e nare then
l i Z K . I l u t t t ~ al n d H . F o r k l . ( ' h c n ~ th,r.. 1 0 5 ( 1 9 7 2 ) 1 6 6 4 . removed by evaporat~on,a d d i t ~ o no f m o w concentrated hydro-
.
1;3 P ' l ' d u c h n t ~ rA I I ~H . Hutt,<.l.('hi,rn 1jr.r 1 0 7 (1 9 7 4 ) 37fi I .
chlor~ca c ~ dand then further cvaporat~on.' r h ~ sprocedure IS
6 4 I<. IIutLcl. P. l'auchnt'r a n d 11. l+'orkl. ('ltc,rtt H v r 1 0 5 (1!172) 1 ..
6 5 . H. S c t r m i d h a u r . . l . K . hlnndl, C'. l*:. X r ~ z r w r L). . F . van dt'r V o n d ~ aI n d C;. P. repeated t w ~ wto ensure complete rcmoval of ox~dr.so f n ~ t r o -
v d r ~d c r K(,lr.n. .I Chc,m. S,,c , ('hvnl (i)rnrr~trrt.,(1976;) 1 7 0 .
6fi 1'. hldchrricr, M . Itvdil a n d P. Cornil, ( ' H . l m d Scl. Sc.1. ;l ,lit 21i2H ( l 9 6 6 ) 6 5 0 .
gen [l].A l t e r n a t i v e l y , d ~ s s o l u t i o nof gold by chlorme or h y d r o -
l n i ~ r g .N I I C ~('h<,rn.
. I ~ , l l . .,3 ( 1 9 6 7 ) 21 5. gen peroxide in hydroc*hlorichi m d 1 s occas~onallyused 141 . I t
6 7 F'. Mdc111ni.r. A ~ ~ ~ ~ l l l r / ' o r, .21 ~ c l(1 l 1 0 2 5 . ,l lrlore. .Vltc/ ('hc~rn , 3 0
i s , o f course, p o s s ~ b to l ~ d n a l y w gold 111 tht>form o f other
(I9fiX) 2 6 2 7 .
6 8 (;. A . E3ownrakc.r a n d R . Whiting, Arrsl J C'hc,m 2 9 ( 1 9 7 6 ) 1 4 0 7 .. complevts than [AuCl,] and examples w i l l he found I n later
(ill A. Sasane. 1'. M a t u ( ~I). , Nakdrnura a n d M . K u h o . J. .Zlnpr~.K e s o m . 4 ( 1 9 7 1 )
257.
sectmns of t h ~ chapter.s
7 0 .J. R c ~ n h o l d 11. , Z w a n ~ i g v r .1.:. H o v c r a n d C . 7,wan~igc.r.%. C h e m . . 1 4 ( 1 9 7 4 ) Another gc.neral t e c h n ~ q u e w, h l c h is w d c l y used I n analysis
3 1 4 ; H . %waii/igcr, .l. R r ~ n h o l da n d Is:. H o y r r . %. Chc.111.. 1 4 ( 1 9 7 4 ) 4 8 9 . for gold, 1s solvcwt cxtract~on.This may be used to concrntratr
7 1 .J. H r h a n . H . A . W. . I o h n s t o r ~ cn~n d H. J. PutIdc.phatt, u n p u b l i s h e d results.
.
7 2 H. Basch a n d H. B. ( i r a v . I n o r y C'hcrr~ 6 ( 1 9 6 7 ) 3 6 5 . a d l l u t e aqueous solutmn of a gold complex or to sc\parate
7 3 W . H. Mason a n d H. R . G r a v . . l A m ('hem S o c . . 9 0 ( 1 9 6 8 ) 5 7 2 1 .
7 4 11 % w a n , ~ p v r .J . R r m h o l d dnrl I.:. H o v v r . %. Chc,rn.. 1 5 ( 1 9 7 5 ) 6 9 .
gold from ~ n t r r f e r i n g~ m p u r ~ t ~Thus, e s . IIlAuCl,] may bc e x -
7 5 D. H B r o w n a n d W. F. S n u t l i . .l. ('tl(,rr~. S r c . U a l t o r ~7'mn.s.. ( 1 9 7 6 ) 8 4 8 . tracted from s o l u t ~ o nI n hydrochlor~ca c ~ dI n very high y ~ c l d
7 6 W . R. M a s o n a n d 11. H . G r a y . I n o r g C h c ~ r , ~7. . ( 1 9 6 8 ) 5 5 . by such s o l v t . n t s as d ~ e t h y ether,
l ethyi acetate, mc)thyl so-
77 .l. L. H y ~ n I, r ~ o r g .C t r ~ , m . .8 (1 9 6 9 ) 2 0 5 8 .
7 8 A . .I. M c C a f f t ~ r v P. . N S c h a L ~a n d P. .l. S t i v h e n s . .l. A m . C t ~ c , n Soc.. ~. 90 butyl ketontl, i s o - a m y l alcohol and d~chloromethane-tetra-
(19ti8) 5 7 3 0 . hydrofuran [5, 61. T h e organic phase may then he est~mated
7 9 H. Ito. J . F u j i l a a n d K. S a l t o , B ~ r l l .Chr~rn.S o c . J p r ~ . .4 0 ( 1 9 6 7 ) 2 5 8 4 .
8 0 A . K . G a n g o p a d h y a v a n d A . Chakravorty, J. Chem. P h y s . , 3 5 ( 1 9 6 1 ) 2 2 0 6 . d~rectlyby neutron actwition, atomic ahsorpt~onor spectro-
8 1 H.-11. S c h r n ~ d l k t .a n d D. G a r t h o f f , J. A m . C h e m . S o c . 8 9 ( 1 9 6 7 ) 1 3 1 7 ; W.
B e c k . W. P. Fchlharnrnc.r. P. P b l l m a n n . E.:. S c h u i r e r a n d K. Feldl, C h e m . Ber.,
photometr~cmethods 1 2, 3 , 51.
1 0 0 (1967) 2335. Gold can also be concentrated prior to analys~sby chromato-
8 2 W. H. Baddley. .'F Basolo. H. B. G r a y . C. Nolting a n d A . J . P o e , Inorg. C h e m . , graphy using an ion-exchange resm or, in a recent development,
2 (1963) 921.
8 3 A. C h a k r a v o r t y , N a t u r w i s s c n s c t ~ o f t c ~4r ~ 8,(1961) 643. a polymer~cresm containing pendant thiol groups which
8 4 W. R. Mason. J. A m . C h c m . Soc.. 9 5 ( 1 9 7 3 ) 3 5 7 3 ; 9 8 ( 1 9 7 6 ) 5 1 8 2 . selectively complex to gold [7-91. For example, a solut~on
containing gold(II1) can be chromatographed on a hexylthio-
glycollate resm. Interfermg ions such as Ag(I), Hg(I1) and BiJIII)
can then be removed by elutlon with hydrochloric a c ~ dand , which may be weighed directly [ l l , 13, 141. The derivative
fmally t h e gold is eluted w ~ t hthiorea s o l u t ~ o nas the complex
[Au{S C(NH,), ,l+ and estimated by spectrophotometry.
Enrichment factors of 108-10" have been obtained by
chromatographic. methods [ 8 ]
In the following s w t ~ o n as brwf mention w ~ l be l made of
the methods used for analys~so f gold in c'hemical laboratories.
It would not he appropriate t o give detailed recipes here, and
only the o u t l ~ n of
~ s thc m ~ t h o d sw ~ l he
l given 'I'he traditional
fire assay method of analysis of gold In ores is used only in
spec.ialist lahoratorics and has b w n cxtrnsively rcv~c.wrdclsr-
where (101 It will thtmlfort- I-K. omi ttcd h r w
(a) G r a c ~ ~ r n c t rtncthods
w / l 11
Most gravimctric methods for gold art1 b a s d on reduction
of a gold-containing compound to thc. mc~taland weighing t h e
gold in this form. If gold is p r r w n t as [AuCI,] , reduction
with oxalic acid, sulphur dioxidr, hydroquinone or sodium
nitrite is most c-ornmon, thv prvfm-rtl method depending o n
the interfering ions present. Formaldehyde, hydrazine salts
and hypophosphorous acid arc uscd less commonly. The dis-
advantago of this gtmeral method is that t h e gold may be
formed in a finely divided statc which adheres strongly t o tho
vessel in which it is precipitated. Thus filtration and transfer
may be difficult.
It is also possible. t o prr>cipitatcgold quantitativcrly as in-
soluble complexes. Thcse are often of uncertain composition
as when citarin, dimethylglyoximc o r 8-quinolinol are used as
precipitants. The compounds are then filtered off and ignited
t o gold metal. Other complexes are precipitated in pure form
and may be weighed directly. Thus stable salts of [AuCl,]- or
[ A u R r , ] are precipitated by bulky cations such as N - ( N - b r o n ~ ~ l
C-tetradecylbetainylW-tetra-decylbetain bis(trimethy1)hesil
methylenediammonium or 2,4,6-triphenylpyrilium [ l , 1 1 , 1 2 1
Derivatives of sulphur-donor ligands may also be suitable.
Thus thioglycollic acid, thiophenol, di-2-thienylketoxime ant1
m-phenylenebis(1-tetrazoline-5-thione) all form derivatives
of Reinecke's salt Au[Cr(NH,),(SCN),] has also been used
[Ill.
( b ) Titrimetric methods [ l , 21
Most titrimetric methods for gold depend on reduction of
gold(II1) t o metallic gold. For example, hydroquinone reduces
gold(II1) t o gold rapidly and quantitatively. The titration may
be carried o u t using indicators such as 0-anisidine o r benzidine
t o determine the endpoint o r by potentiometric titration.
Alternatively, cxc-t.ss of hydroquinonr. may bc added, and the
txcctss hack-titrated with ci~rium(1V)[l51.Mcthods bascd on
reduction o f gold(I1I) t o gold by iron(II), titanium(III), oxa-
latc or ascorbic acid have also h e m doscribtd [l].
Reduction of gold(lI1) to AuI by excess of iodide, with
titrimctric estimation o f the rel(.asrd iodine, is the basis of
another method, while clstimation o f thc cyanide uscd in
oxidation o f gold t o I A u ( C N ) , ] by air has also been used t o
determine gold.
( c ) Spctrophotornetric methods 12,iil
Spectrophotometric methods are particularly useful when in-
sufficient sample is prcsent for the gravimetric or titrimttric
methods. Although intcrfrrence by other metal ions is often a
serious problem, suitahlc systems have been deve1opt:d for
analysis of gold in the presence of most of the likely impuri-
ties.
The simplest method is t o convert t h e gold complex t o
[AuCl,]- o r [AuBr,] in aqueous solution and t o measure the
absorbance d u e t o these ions. Many impurities interfere, how-
ever, and it is usual t o extract the [AuCl,] o r [ A u B r , ] into
an organic solvent before measuring the absorbance. In di-
chloromethane-tetrahydrofuran t h e species present is thought
t o be [thf-H]+[AuCl,]-, while in chloroform containing tetra-
phenylarsonium chloride t h e ion pair [Ph,As]+[AuCl,]- is
formed 1.5, 61.
 In other methods, varlous reagents can be added t o form
coloured complexes of gold and these are then estimated spec-
trophotometrlcally. One popular reagent is rhodanine which
forms an ~ntenselyred complex with [ AuCl,]. In aqueous
solution the complex 1s formed as a colloidal suspensloll and
thv cwlour is unstable, but this problem can be overcome by
solvent rxtract~on[ 5 ] , or by add~tionof pyr~dint,since the
complex 1s soluble in aqueous pyridine 1161. rhe number of
other reagents L ~ S is
C ~too n e a t to allow detailed discussion
[AuCI4] , HCI
[huC14J , HCI
[AuC:141 , IiCl
[AuC14[ , HCI
A u ( I I I ) , alkalint.
[AuCI41 , HCI
[ l -3, 51, but somt. are included in Table. 11.1. Most methods
rely on extractlon of the cwloured complexc~sInto an organic
solvent, a procedure whlch often separates gold from interfer-
ing ions and which can concentrate the gold-containing species
and thus make poss~blethe analysis of very dilute solutions of
[AuC1,]-.
A related method is based on ox~dationof luminol by
[AuC14]- and observation of the resultant chemiluminescence.
The luminescence is however suppressed by ions such as thio-
cyanate [26].
( d ) Electrochemical methods
These methods are not often used, but ion-selective electrodes
with high specificity for [AuCl,] or [Au(CN),] have recently
been developed and the method may become more popular as
a result [27]. The liquid ion-exchange electrode recommended
for [AuCl,] is based on bis(4-ethyl-3,5-dipropyl-l-pyrazoly1)-
methane 1271. Several ions including Zn2+and Ag' interfere.
( e ) Atornic absorption and emission spectrography
Atomic absorption spectrophotometry is becoming a partl-
cularly popular tti-hnlqut for determination of gold in trace
quantities [28, 291 Thus, using a carbon rod atomiser, concen-
trations of gold in aqueous solut~onof about 1ppm can be
estimated accurately 130, 311, and considerably lower concen-
trations can be analysed if atomic absorption 1s used In con-
junction with conccntratlon of gold by solvent extractlon or
chromatography 12). lJslng chromatographic concentration
and emission spectroscopy, concentrations of gold in sea-water
In t h region
~ of 1 0 l 2 ppm were determmed to an accuracy
of about + 10% [ 8 ] .
( f ) Neutron activation
This is the most scnsit~veanalytical method for gold and is
the preferred technique when gold is prrwnt in very low con-
centrations as in sea-water or meteorites 14, 71. The great
sensitivity arises since ' A U is the only naturally occurring
isotope of gold and has a high ntwtron capture cross section of
9 8 barns. The product '"AU decays by P- and y-emission with
a half-l~fcof 2.7 days. Again, the gold is normally concentrated
and separated from impurities by solvent extraction or chroma-
tography prior t o analysis 12, 4, 7, 32, 3 3 ) .
BIOL0C;ICAL APPLICATIONS O F G O L D [ 3 4 ]
Although gold has been administered since the earliest times
for the cure of all diseases, with the aurum potabile of the
thirteenth century perhaps being the most famous cure-all, it
is only recently that a sound basis for gold chemotherapy has
emerged. The chief uses are of various gold(1) thiol corny,unds
in the treatment of rheumatoid arthritis and of radioactive
"'Au in radiotherapy.
(a) Gold in the treatment of arthritis [35, 361
The gold compounds which are presently used in the treat-
ment of rheumatoid arthritis are shown in Table 11.2, and their
use is generally known as chrysotherapy. Other compounds
such as Na,[Au(S,O,),], known as Sanocrysin, have formerly
been used and these drugs were also used in the period 1925-
1935 in the treatment of tuberculosis.
The gold(l) compounds are administered intramuscularly
and appear t o be as effective as any other known drug for
treatment of arthritis, though toxic side-effects are often a
problem [37].
In the evaluation of new gold drugs, it is customary to test
if the drug suppresses adjuvant arthritis in rats, since there is a
TABLE 1 1 . 2
strong similarity between this disease and rheumatoid arthritis
in humans. Although there is some disagreement [38], control-
led tests show that sodium gold(1) thiomalate does suppress
both the primary and secondary lesions of adjuvant arthritis
in rats, although it has little effect when given therapeutically
after arthritis has begun 139, 401.
A disadvantage of the present chrysotherapy drugs is that
they must be administered parenterally in doses of about
50 mg per week, and it is difficult t o control toxic side-effects
which may continue for a considerable time after chrysotherapy
is discontinued. An orally administered drug has considerable
advantages in this respect, and a number of trialkylphosphine-
Somr- Ivrtiary phosphint, compl(.xt,s o f fiold(1) with anti-arthritis propertirs
C'HLC'O,II
1 (rrf 45)
Et$ Au S C11C02H

Commonly used gold(1) drugs

Et>
Chemical formulau Chemical name Trade name
I
S Au P,
-- p---- ---p-- , \
CII: CH,
Au--S -CHC02- ~ a + D ~ s o d ~ ugoltl(1)
I
m th~omalatr Myocrisin 1
CHL
/
CH2
(rrf 4 6 )

P' Au -S/'
I
Et2
CHIOAc
Solganol
(*c-ytpEt , (rvr 4 4 )

AcO

T h e detailed structures are n o t known. The compounds may be poly 0 Ac

meric like other complexes (RSAu),,.
gold(1) complexes have recently been shown t o suppress
adjuvant-induced arthritis in rats and t o give a high serum gold
level. Some of the more effective reagents are shown in Table
11.3. The effectiveness depends primarily on the phosphine
ligand, with triethylphosphine being most effective, but also
on the anionic group. The role of the tertiary phosphine is
probably t o enhance the lipid solubility of the gold drug and
so t o facilitate its absorption and distribution in the body.
Also as a result of the different solubility properties, the
distribution of gold throughout the body is different from
that rcwdting from administratior1 of the conventional water-
soluble gold drugs. In particular, concentration of gold in the
kidneys with resultant harmful effects is considerably less for
the phosphine complexc~s,and it is likely that the new phos-
phinc-gold drugs will hc usvd thcraprutically in the not too
distant future.
( b ) Thr. rncchanisrn of a(-tion of gold drugs
Studies using rad~oac.twcly1al)tlllcd gold(1) thlomalate show
that about 2070 of the gold is t..tcreted in the first two weeks,
but that after this time furtht>rcxcrction is very slow. Gold is
concentrated in the inflamtd joints and probably acts by in-
hibiting enzymes mvolved in thc Inflammatory process \ 47,
481. Certainly, there is considerable cvldence that gold(1)
thiomalate inhlb~tssuch enzymc.s as acid phosphatast,
0-glucuron~dast~, c.athepsin and glucosamine-6-phos[)hatc
synthetase and, it is suggested, that there may be a general
effect on SH-contalnlng c3nLymcsarising through cw-ordination
observation that after administration of gold drugs labelled at
both the gold and sulphur atoms, the distribution of radio-
active gold and sulphur in the body is not identical [55], show-
ing that cleavage of the gold-sulphur bond occurs in vivo. Both
exchange and further co-ordination of thiolate to gold have
been demonstrated by '% n.m.r. spectroscopy, 2nd evidence
for formation of the cluster [Au4(thiomalate),13 in the pre-
sence of excess of thiomalate has been obtained [56, 571.
Further evidence for the interaction of gold with thiol
groups is obtained by X-ray diffraction studies of crystalline
proteins and enzymes containing a gold complex. The heavy
gold atom is used to enable solution of the phase problem
associated with determination of structures by X-ray methods.
The complex ions [Au(CN),I-, [AuCl,) and [Au14]- are
frequently used, but it is possible that substitution of a halide
ion or reduction t o gold(1) may occur in the presence of the
protein or enzyme. Some cxamples of structures investigated
by this method are given in Table 11.4, and it will be clear
that gold is often associated with the amino-acid cysteine which
contains an SH group.
In conclusion, it is shown that gold(1) thiol derivatives can
undergo exchange with free thiols, that gold has a high tend-
TABLE 1 1 . 4
Gold d~rivativeso f rnLymrs and protcins [ 3 4 ]
Gold I,ibelhng agent Protr~nor enzyme Gold h~ndlngs ~ t e Ref.
---- -- --. -- --- - --

of the thlo group t o gold [49-541. Thus the inhibition may [Au(CN)21 Flavodox~n Cyste~ne
not be observed in the presence of SH protwting groups or by L~veralcohol Cyste~ne
dehydrogenase
addit~onof other SH-contaming compounds such as cysteine [AuC14]- Cytochrome c2 Histidine
or DL-peniclllamme (49, 531, which can compete successfully Lysozyme Arginine
for the gold centre. Myoglobin Histidine
For thls kind of behaviour to be observed, it 1s necessary Haemoglobin Cysteine
that gold(1) thiomalate should be able to react with more thiol Lactate dehydrogenase Cysteine
IAuI41- Myoglobin Near haem
or that exchange between CO-ordmatedR S and uncomplexed
Chymotrypsin ?
RSH should occur readlly. Exchange is demonstrated by the
ency t o bind t o sulphur-containing groups in enzymes and
proteins, and that gold(1) thiol drugs inhibit enzymes in which
a free SH group is necessary for activity to be observed. Thus,
the circumstantial evidence that gold therapy in arthritis
treatment is successful due to inhibition of thiol-containing
enzymes which cause the inflammation is strong, and it is
likely that direct evidence on this matter will be sought in the
near future.
( c ) Other biological effects of gold
Gold therapy may have harmful or beneficial side-effects.
An example of the latter is given by the anti-histamine prop-
erties of gold(1) thiomalate, which is present in the therapeutic
concentration range during normal chrysotherapy treatment
[66]. Gold drugs also have beneficial effects against Myco-
plasma and Leishmania 1661.
Also potentially inkresting is the observation that [AuCl,]-
forms a complex with DNA probably by co-ordination of
nitrogen atoms of amino-acids 1671. This could interfere with
cell division and indicates that gold(II1) complcxes may be
found to have anti-cancer properties. Thus the complex cis-
[PtC12(NH3),] is thought t o have anti-tumour properties due
t o co-ordination of DNA t o platinum. A preliminary report
suggests that [A~Cl~(5-diazouracil)~]*Cl does indeed have ant'
tumour properties [68]. It is also known that gold(1) thioma1al.1-
inhibits DNA synthesis in sheep lymphocytes [69]. Further
exciting progress in this area is obviously possible.
( d ) T o x i c i t y of gold (54, 701
Labelling studies have shown that gold(1) drugs are concen-
trated in the kidneys and, t o a lesser extent, in the thymus,
liver, spleen and hypothalamus [71, 721. The precise distribu-
tion is dependent t o some extent on the particular compounds
administered. The concentration in the kidney can be particu-
larly serious and may result in dermatitis, stomatitis, thrombo-
cytopenia and renal damage [73].
Gold toxicity may be treated by injection of chelating agents
which hasten t,he excretion of gold from the body. Recom-
mended for this purpose are DL-penicillamine and British anti-
lewisite (BAL), both of which contain SH groups which are
particularly effective towards gold(1) [72, 741. Also recom-
mended is treatment with prednisone and corticosteroids
generally [74, 751.
Although the overall toxicity of gold(1) thioglucose is no
greater than that of the thiomalate, the former leads to con-
siderably greater concentration of gold in the hypothalamus
of the brain [76, 771. In animal studies, this is found to result
in obesity and hypcrphagia in mice and guinea-pigs and to brain
damage in rats [76--801.
( e ) Applications of rudiouctiue gold in medicine
Radioactive "'AU finds use in medicine in radiotherapy.
Cold may be in the form of grains which are placed where
required or sometin~esin colloidal form. Colloidal '"Au is
used in radiotherapy of pleural or peritoneal effusions and
bladder cancer where an insoluble radiopharmaceutical capable
of uniform radiation of irregular surfaces is required [81].
Colloidal '"Au is also used for various diagnostic purposes,
for example in bone marrow scanning or in delineating the
lungs and liver. The colloidal gold is taken up by the organ
which can then be observed by scintigraphy.
CATALYTIC PROPERTIES O F GOLI)
Gold is generally regarded as being the least useful of the
nnble metals for catalytic purposes. The low catalytic activity
of gold is due t o the d-band being filled, with the result that
gold is unable t o chemisorb small molecules. Thus hydrogen
is not adsorbed by gold a t temperatures below 473 K (above
this temperature, thermal excitation of electrons from the
d-band t o the 6s-band occurs) and ethylene is adsorbed only
weakly.
 If gold is to be used as a hydrogenation catalyst, it is there-
fore necessary t o supply hydrogen atoms for reduction at the
gold surface. This can be effected either electrolytically or by
the gold-catalysed decomposition of formic acid, but neither
method is attractive. Better results have been obtained by using
very finely divided gold particles on alumina or silica supports.
Such small metal crystallites become electron-deficient, and
their properties then resemble those of the preceding element
in the Periodic Table, so that very finely divided gold particles
take on some of the properties of platinum metal [82]. In
accord with this theory, the supported gold catalysts, which
are usually preparcld by heating Fl[AuCl,] adsorbtd o n the
support material, are able to catalyse the hydrogenation of
alkenes, alkynes and dienes under conditions where massive
gold is inactive. These catalysts also effect exchange between
deuterium gas and hydrogen atoms present in the support
material. Thus, in the catalytic hydrogenation of hutadiene,
it is suggested that butadiene is adsorbed onto the gold and is
then reduced by hydrogen atoms which migrate from the
support to the metal surface 183, 841.
Gold films prepared under ultra-high vacuum have been
shown to catalyse exchange between hydrogen and deuterium
groups of MeSiH, and MeSiD,, apparently by reversible loss
of H, or D, from the chemisorbed molecules with formation
of chemisorbed MeSiH or MeSiD species [85]. Gold is also a
catalyst for isomerisation and hydrocracking of hydrocarbons,
but is less effective than other noble metals. One interesting
example is the catalysis of the isomerisation of the complex
strained-ring molecule diademane to snoutene and then t o
basketene by gold [86]. Some reactions of oxygen are also
catalysed by gold, for example the oxidation of propene t o
propene oxide and of methanol t o formaldehyde [87].
Gold is also frequently used t o modify the catalytic
properties of another metal [88]. Often, gold decreases the
reactivity but increases the specificity of the catalytic reaction
For example, addition of gold t o platinum or iridium surfaces
gives increased selectivity t o the isomerisation of iso-butane
rather than t o its hydrogenolysis [89], and a gold-palladium
catalyst has greater specificity for isomerisation of a-pinene
to P-pinene and for oxidation of ethylene to acetaldehyde
than has palladium alone. Interestingly, the isomerisation of
2-methylpentane t o 3-methylpentane occurs predominantly
by a different mechanism with a Pt catalyst than with the Pt-
Au mixed catalyst, as demonstrated by labelling studies [go].
'1-Au
,/
adsorbed
112
Exceptionally, the addition of gold t o palladium has little
effect on the selrctlvity towards the catalytic isomerisat,ion or
cracking of hydrocarbons though the reactivity is drcrcased
[go]. Addition of gold t o rhenium enhances the catalytic
properties, for cxample in the conversion of C,, hydrocarbons
to benzene 1911.
Gold compounds may also have catalytic properties, either
alone or in conjunction with a scxond transition metal com-
pound. For example, the manufacture of vinyl acetate from
ethylene, oxygen and acetic acid is catalysed by palladium
acetate on silica or alumina promoted by EI[AuCl,] or, prefer-
ably BaAu,(OAc), [92].
Some catalytic reactions are based on the oxidising ability
of gold(II1) complexes. For example, acetylene is oxidised to
glyoxal in water-acetonitrile by [AuCl,(YPh,)].
HCCH + 2[AuCl,(PPh,)] + 2 H 2 0+CI10. CH0 + 2[AuC1(PPh3)]
Since [AuCl(PPh,)] can be oxidised back to [AuCl,(PPh,)l by
chlorine or tetrachloro-o-quinone, the system can be made
catalytic and yields of 250% based on gold have been obtained
[93]. Primary amines are also oxidised t o ketones or aldehydes
by gold(II1) complexes [94], and alkenes can be converted t o
epoxides by [AuCl(PPh,) 1 and 0 apparently by a free-radical
mechanism [95, 961, but none of these systems is yet attractivv
commercially. Gold(II1) complexes can also be used stoichio-
metrically for the oxidation of alkenes, alkynes and cyclo-
propanes [96b]. Cyclopropanes are first isomerised t o alkenes
which then g i k 1,2-adducts. Other catalytic. reactions are the
hydrogenation of alkencs with AIL(III)-S~bonded complexes
[97], the dimerisation of acrylonitrile to adiponitrile using
[AuBr(PMe,)l and sodium amalgam [98 1, the metathesis of
alkenes using [AuCl(YPh,)] and organoaluminium cwmpounds
[99] and the decomposition o f diazoalkanes by [AuC13(pyri-
dine)] [ l o o ] . The catalysis of conversion of isocyanides t o
formamidines was discussed in Chapter 7.
In conclusion, neither gold nor gold complexes have been
used cxtrnsivcly as catalysts in t h past
~ but rvcrmt research
suggests that their use is likely t o increase in thc? future.
METHODS O F GOLL) COATING
One of the most rapidly expanding uses of gold is in the
electronics industry. Gold is used in switching devices and in
micro-electronic circuits. For thcse purposes, gold is usually
plated onto another material electrolytically. The nature of
the gold deposited is critically dependent on the nature of the
electrolyte solution used. Most such solutions are based on
K[Au(CN),] which may be used in acid, neutral or alkaline
conditions, but solutions based on thiosulphate or sulphite
complexes of gold are also used [ l o l l . It was originally thougill
that gold was deposited by direct reduction of adsorbed
[Au(CN),]- but it now seems that the reducible species is
AuCN which is present in very low concentration in equilibrit~t~t
with [Au(CN),]-. Only at high overpotentials does reductioll
of [Au(CN),]- occur [102]. Gold is also used t o connect com-
ponents in micro-electronic circuits. For this use, various gold
pastes may be used, or gold may be deposited by the metal
sputtering technique from the vapour phase. The technology
involved in the various uses of gold in electronics is now
extremely sophisticated, with the need t o use the minimum
quantities of gold being a particularly important factor.
Gold is also used t o decorate glass and ceramics. Here,
another technique for producing thin, strongly adhering gold
coatings is t o adsorb a solution of a gold compound onto the
surface and then to pyrolyse the compound t o gold. Recom-
mended for this purpose are such compounds as gold(1) thio-
lates and phosphine complexes of gold(1) [103, 1041. Where
particular designs are required the "liquid gold" solutions can
be painted onto the pottery or glassware.
OTHER APPLICATIONS OF GOLD
Applications of gold which do not primarily involve its
chemical properties will be reviewed only very briefly. The
chief uses are as a monetary standard, in jewellery and in
dentistry. The infrared reflectivity of gold leads t o its use in
the aeronautics and space industries, and its low chemical
reactivity leads t o use in lining specialised chemical plant and,
alloyed with platinum, in the production of viscose rayon. It
is encouraging t o the chemist that the fastest growing uses of
gold are in industrial rather than decorative applications
[105].
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8 3 G. C. Bond, P. A. S e r m o n , G. Wehh, D. A. Burharian a n d P. B. Wells. J. Chc,nt
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GOLD-ELEMENT BOND LENGTHSa
134.
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A. GOLD-HALOGEN BOND LENGTHS
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9 2 H. F e r n h o b , F. Wunder a n d H. .l. S c h m d t . Ger Pat., 2,087,087, 1972: C'hcrn
,\hstr.. 77 (1 9 7 2 ) 8 7 8 9 7 : S. S c h ~ , t t .D. W. Lum drld I. I,. Mador. (:rr Pat.. terminal A u F distance 1
2.420.374. 1 9 7 4 : ('hcm ,A hstr.. 8 2 ( 1 9 7 5 ) 90f559. bridging A u F distance
9 3 K. A. C. Rrnnle. Brit. Pal.. 1.071.YO2, 1 9 6 7 ; Chcm. Abstr.. 6 7 ( 1 9 6 7 ) 5 3 6 8 5
2
94 M. E. Kuchne a n d T . C. Hall, .I. Org. ('hvrn.. 4 1 ( 1 9 7 6 ) 2742.
9 5 A. Fusi, K. U g o . b'. Fox. A . Paslni a n d S. Ccnlnl. d O r g a n o m ~ t .('hc,m., 26 hridging AuCl 3
( 1 9 7 1 ) 417. bridging A u ( 1 b C I 4
96 K. Masada a n d A. Y a w l , .lapan I'af.. 71 09.69 1. 197 l : ( ~ h c r nA hatr.. 7 5 hridging A u ( I I I b - C l
(1971) 19786. terminal A u ( I I 1 F C I
( b ) R. 0. C. Norman. W. .I. E. Parr a n d C. H. Thonias. J (Ihrm. Soc.. Prrkirl
'I'rans. 1. ( 1 9 7 6 ) 1983. hridging Au(III)--Cl 5
97 M. C. Muller. Gold Hull.. 7 ( 1 9 7 4 ) 39. terminal Au(ll1)- Cl
9 8 K. Y a m a m o t o a n d M. Kawaniata. J a p a n 1'01.. 71 16.730. 1 9 7 1 : ('h6.m. Abstr in [AuC12j- 6
7 5 ( 1 9 7 1 ) 64570. in [AuCI4]-
99 D. H. Kubicek a n d E. A. Zuech, [!.S. Pnt., 3.558.520. 1 9 7 1 : C h r m . Abstr..
74 ( 1 9 7 1 ) 99441. 7
1 0 0 M. G. Krakovyak a n d S. S. Skorokhodov. Vysokomol S o ~ d i n . Scv. . A., 1 1 8
( 1 9 6 9 ) 794. 8b
1 0 1 R. T. Page, M u l Fintxh. J . , 2 0 (1974) 87 a n d 122. 9
1 0 2 .I. A. Harrison a n d J. T h o m p s o n . k'lrctrochrm. Acla.. l 8 ( 1 9 7 3 ) 829.
1 0 3 H. M. Fitch. 1 3 ~ 1Pal., ~. 6 2 1 , 886, 1973. 9b
104 l?. M. P o t r a f k r , IJ.S. Pat.. 3.625.755, 1 9 7 1 : (Ihrjm. Ahstr.. 76 ( 1 9 7 2 ) 62691 trigonal planar,
1 0 5 1). Lloyd-Jacnb. Gold Ijull.. 4 ( 1 9 7 1 ) 25. LCIAUP = 1 18.7' 10
[AuCI(P- P)] three-CO-ord.gold(1)
I C I A u P = 90.4,
93.4' ll
12
13
trans t o C1 14
trans t o PPh,
trans t o CbFS 15
trans t o SPr2 16
trans t o Ph
distorted square 17
pyramid, t r a m to
C1
trans t o N
" F o r abbreviations, see p. 266.
APPENDIX A--continued

Compound r(AuX)lpm Comments Ref.

Compound r (AuX)/pm Comments Rrl. P

distorted square 18 r(AuS) 32

pyrarmd, t r a t ~ st o 33
CI S-bonded sulphite 34
lruns t o N 9
distorted square 19 trigonal gold(1) 35
pyramid, axial 16
Au--Cl asymmetrically bonded 36
gold(I1) complex 20 dithwcarbamate
r(AuBr) 2l 37
22 38
45 39
t e r m ~ n a lAuBr (listancc 7 1 40
brdgrng AuBr lruns t o 21
Br bidentate dithio- 4l
hridg~ngAuBr lrut~.\t o carbamate
Me monodentate d i t h ~ o -
trutls t o P and C 23 carbam,~tc,
AuS(d~thiocarham,itc.) 4 2
l r i ~ n st o P 2:$ AuS(mn1)
lrans t o C AuS(dith~ocarbamate) 4 3
distorted square lH AuS(mn t )
pyramid, trans t o 44
Br br~dgingA u S t 45
tram to N r ( A u T t ) calavtrite 46
bridging iodide 24 r ( A u T c ) In k r e n n e r ~ t e 4 6
tetragonal gold(II1) 25
cluster complex 26
gold(I1) complex 27 C. (;OLD--GROUP VB ELEMENT BOND LEN(:THS
carbene complex 2H
Compound r (AuX)ipm Comments Ref.
-
~--p--p

B. GOLD-GROUP VIB ELEMENT BOND LENGTHS [ A U ( C C P ~('P~NH,)]

) 203 47
[AuCl(piperidine)l 206.8 8b
[ A u ( ~ ~ )(PPh.dl
PY [PFd 21 6.6, 221.2 distorted-trigonal 48
Compound r (AuX)lpm Comments RVI gold(J)
[ A U ( N H J ) ~[No31
] 3 202 49
[ e n ~ ~ l ~ [ ~ u ( ~ 0 3 12-
)2(en) 211.9, 213.3 34
[AuC1(Ph4porph )] 200 av. square-pyramidal 19
gold(II1)
[ { A ~ ( c P ~ = c P ~ c P ~ & P ~ ) o H } ~ ] 223,226 bridging AuO 31 [AuC13(2,9-dimethylphen)] 209 t r a m t o C1 18
APPENDIX C conlmued D. G O L I t C A R B O N BOND LENGTHS

Re1 ---
Compound r(AuX)/pm Comments
Compound r(AuX)lpm Comments Ref
258 axial position of square
pyramid [Au(CN)zI- 21 2
[AuBr3(2,9-dimethylphen)] 208 trans to Br 18 [Au(CN )(PPh3)1 185
261 -
axial nitrogen [Au(CN)(MeNC)] 201 r (AuCN)
r ( AuCNMe)
lrans t o Cl
axial nitrogen

bridging carbon

r(AuMe) truns ylid

r(AuMe) lrans Me
r.(AuCH2)
t r a t ~ st o P
trarls to Me
lruns to C1
lrrrns to P

238.2
221.2
232.3
227.5, 228.3
227
230.7, 231 .O
229 Au(1kP 23
230 Au(1IIkP Au(IkC 60
221-229 cluster complex Au(IIIFC(CF3)
2 30 cluster complex Au(II1F-Me
227.4-231.1 cluster complex carbene complex 28
233.5 gold(I1) complex 20
250 gold(I1) complex 27
235 mean value 66
237 mean value 66
69
tetrazolato complex 70
71
 266

E. GOLD-METAL BOND LENGTHS

Compound Comments 1 F. M. H IElnsteln. P. K. R a o , d. T r o t t e r a n d N . Bartlett. J . ('hc~rn.S o c .a. ( I g ( i 7 )

478.
Au cubic close packed 2 A .l. E i l u d r d s a n d G. R. J ( ~ n e s J. . Chc,m S o c . A ( 1 9 6 9 ) 1 9 3 6 .
3 F:. \l. \V . I a ~ i s s r n ..l. C . W F o l r n r r a n d G. A . h ' l r g ~ w .J 1 . c (~' o r n m o u .ll,st..
Au2 gas phase only 3 8 ( 1 9 7 4 ) 71.
[{Au(S~CNP~?)}~] r ( A u A u ) intra- 4 D. H. Dell',41nlco, F. C a l d e r a / / o . F. h l a r c h e t t ~ .S. Mvrlinu a n d G. Perego,
molecular .I. ('111.m Soc.. ('hem. C ~ ~ m r n u r( ~1 9. ,7 7 ) : < l .
r ( A u A u ) inter- 5 E. S. Clark. D. H. T e r n p l r t o n a n d C. hl. M r G ~ l l a v r y ..4cla C ' r ~ s t a l l ( ~ p r1. .1
(I 9 5 8 1 2 8 4 .
molecular S J C. M. T. Eijndho>c.ri a n d G.C. Vcrschuor. .\lulc~r.l i c ~ s l$uii.. 9 ( 1 9 7 4 ) 1 6 6 7 .
r(AuAu) 7 N . C Barntiger. E. Hc.n!i<.tta n d I). hl. S o b o r o f f . Ac.tn C'?-vstullrrgr., B 3 2
r(AuAu) (1976) 962.
J-( AuFc) R Cr. .I Arai. K,,,.7 ' 1 1 1 , . ( ' J I I ~ I'uvs l l m 81 ( 1 9 6 2 ) 3 0 7 .
:b) .l. .I. G u k . P. G. . I o n c a . hl. .I. Mdvs d n d G . 51. S h c l i l r ~ c k .J . ('ti(,nl. Soc..
D a l t o r ~ I'rarls., ( 1 9 7 7 ) 8 .
9 ( a ) M. G. B. 1)rew ,incl M. ,I. I<lt.dl. .I. ( ' l i ~ ~ mSo<,.. 1lrilto11 T'rans.. ( 1 9 7 3 ) 5 2 .
(h) H. S c h ~ n l d b a u r .A. W o h l l c l ~ t ~ nF.. Wagnt,r. 0.O r a m d a n d G. I i u t t n c r . C'hvm
Rev., 1 1 0 ( 1 9 7 7 ) 1718.
1 0 N. C. Harn/~gc.r,K M . I)ittc,n~c~rv d n d .l. K . I)ovlc.. Irlorc Chc,rn., 1 3 (1 9 7 4 )
hlran centre to peri- 805.
phery 1 1 M. Bnrrow, 11. B. Bu~.rgl. D. K . .Johncon a n d I,. M. V r n a n ~ i J. . Art1 ( ' I I ~ ~ JS(J<,., II
Mean r ( AuB) 9 8 (1 9 7 6 ) 2.3.56.
1 2 P. G. J o n c s . .l. J. G u v dnrl G M . S h e l d r ~ c k ;, I ~ . l u( ' r \ . \ l a l l o ~ . r - B31
.. (1975)
Mean r ( A u B ) 2687.
r(AuW\ n ~ A . L,. K o d ~ c . r s .. Z I . / O ('r\,slulloirr.. B31 (1 9 7 5 )
1.3 M . R ( ' s l r ; ~ ,l.. R . N a s s ~ r n h t ~dnd
r (Auhln) 1112.
r(AuW) 1 4 G. Bandoll. I). A . Clt31nentr. G . M a r a n g o n ~a n d L. Cattallni. J ('hr>m. S o c .
U a l t o t ~Y'rans., ( 1 9 7 3 ) 8 8 6 .
r ( AuCo) 1 5 R. W. Bdker a n d P. .I. Paulirlg. J. C/ilfnl S o c . ('hcnl ~ ' o l l l r l l u ~ l(]!)Ci'J) .. 745.
1 6 M. McPartliri a n d A. ,I. Markwrll. J O r y a f ~ o n ~ oC'h<'rn.. t. 57 ( 1 9 7 3 ) C25.
1 7 K. J. C h a r l t o n . C. M. fIarris. H. I'atil d n d N. C . S t c p h c n s o n . I r ~ o r g .Yucl Ct1c.m
1,r~ft..2 ( l 9 6 6 ) 4 0 9 .
ABBREVIATIONS .
1 8 W . T . Rohlrison a n d l.:. SIIUI..I C'hc.~rl S f j c , 1)uiton 7'rufls ( 1 9 7 5 ) 7 2 f j .
1 9 K. T ~ n i k o v l c hd n d A. Tulmskv. I r ~ o r ~( ,.' I I I ~ ~ 1I .6. ( 1 9 7 7 ) 9 6 2 .
, K . Mancll. A . Frdnk a n d G. H u t t n r r . ('hc2m H<,!-..1 0 9 ( 1 9 7 6 )
2 0 If. S r h n i ~ d b a u r .l.
466.
B~PY = 2,2'-bipyridine
2 1 P. T. Reurskrns. H. .I. A. Bladuw. .J. A . Crdb d n d .l. .l. Steggerda. I n o r g C'hern..
Bu = butyl
7 (196 8 ) 805.
Diars = 1,2-bis(dimethy1arsino)benzene 2 2 F. W. B. E ~ n s t e l na n d I t . K c s t ~ v o .4cla
, ('ry.slallo~.r.. B31 ( 1 9 7 5 ) 6 2 4 .
2,9-Dimethylphen = 2,9-dimethyl-1,lO-phenanthroline 2 3 M. A. B m n r t t , K . IIoskms, W. R. K n e e n . R . S. N v h o l m . P. R. H l t r h c o c k ,
En = 1,2-diaminoethane R. Mason. G. B. K o b r r t s o n a n d A . D. C. Towl. d A r r ~ ('hcrn Soc.. 9 3 (1 9 7 1 )
4591.
Et = ethyl
2 4 A. W e ~ s sd n d A . W<.iss,% R'alurfi~rsch.. 1 1 b ( l 9 5 6 ) 6 0 4 : N. J a g o d ; l ~ n s k i .
Me = methyl %. Krhsl.. 1 1 2 ( 1 9 5 9 ) 8 0 .
P-P = 2,11-his(diphenylphosphinometh> 2 5 V. F. D u c k w o r t h a n d N. C . S t c p h c r i s o r ~ .Irr<~rg.( ' h c ~ n ~8. . (1 9 6 9 ) 1 6 6 1 .
phenanthrene 2 6 P. Bellon, M. M a n a s s r r o a n d M. Sdnsonl. J. C h e m . S o c . . D a l t o n I'runs.. ( 1 9 7 2 )
1481.
Ph = phenyl 2 7 .l. P. Fackler. Jr., persondl c o m m u n i c a t i o n .
Ph4porph = cu,o,y,&-tetraphenylporphinate 2 8 Lj. Manojlovlc-Muir, J. Or-pattorn1,1. Chcjni.. 7 3 ( 1 9 7 4 ) C 4 5 .
Pr = propyl 2 9 C. D. G a r n e r a n d S. C. Wallwork, J. C'hran~.S o c A , ( 1 9 7 0 ) 3 0 9 2 .
TCNQ = 7,7,8,8-tetracyanoquinodimethane 3 0 G. E. Glass, .l. H. K o n n e r t . M. G. Milrs. D. B r i t t o n a n d K. S. Tobias. J A m .
C h c m . Soc.. 9 0 ( 1 9 6 8 ) 1 1 3 1 .
31 M. P e t v a u - B o ~ s d c n g h ~ r n.I.. Mrunler-Plrct nnd M. van Mt,ersche. Crysl. Struct. 6 8 M. M<.Partlui. R. Mason a n d L. Malatesta. J. Chcm. Soc.. ( ' h ~ m C o m f r ~ l ~. t !
C'<~mnlun.. 4 (1 9 7 5 ) 375. ( 1 9 6 9 ) 334.
3 2 11. liuben, A. Zalkln. M. 0. I~'al1ensdnd I ) H . Tt'mpleton. Inijrg Chcm.. 1 3 a n R . K . Kvan. Acta Crystallogr.. B28 ( 1 9 7 2 ) 1 6 2 9 .
6 9 R . A . P ~ n r i < ~ m*rid
(1974) 1836. 7 0 W. P. Fehlhammer a n d L. F. Dahl. J. A m . Chem. Soc.. 9 4 ( 1 9 7 2 ) 3 3 7 0 .
3 3 P. G. .l~)ncs..l. .l. (;uv a n d G . M. S h e l d r ~ c k .l c t u C'rvstulloyr., A32 ( 1 9 7 6 ) 3 3 2 1 . 71 S. K < , m ~ v aJ., C. H u f f m a n a n d J. K. Kochl, Inorp. Chem., 1 6 ( 1 9 7 7 ) 1 2 5 3 .
3 4 A. n u n a n d arid I t . ( i r r d ~ l ,:lclu ( ' r ~ s l o l l o i l..~ B31 . (1!)75) 370.
3 5 J. C. Huffnian, K S. Koi.h and A. K . S ~ e d l r .I. 9 m ('hr7m Soc.. 9 8 ( 1 9 7 6 )
4340.
36 .l. G. Wilnhovcn, i V . P. .I. 11. Bosnlan a n d P. ?' Bcurskrns. J ('r?st Mlr~l.SLruct.,
2 ( 1 9 7 2 ) 7.
:17 R. Hess,, dnti P . I t . n ~ ~ ~ s ( . .hI vr ,10 C/rr,m Scarrd.. 26 1 1 9 7 2 ) 3855.
38 S. L. I,dwL<,ll, 1V . l , f t < , h r b a ~ r gnn(l h (; I'. K o k o t n ~ l o /,!oi-g . ('hfam.. 11 ( 1 9 7 2 )
2227.
3 9 P. 'S. Brur5kcris. .l. A ('m> .rntl ,l c;. M wrl dt.r I,lr~dt.r~. I I ~ ~ I ~ ('hr7m..
I,* 9 (1 9 7 0 )
475.
4 0 J . A. ( : r f t h , . l . ki. t \ < ) o r c l ~ P.
k ~ l' t3i,ursk<,11h ~ I I C AI M Vvrh~><,vvn, ,l Crvsl. MiiL
S l r u c l , 1 ( 1 9 7 1 l 155.
.
41 , l . H. X o < > r ( l ~r k,,v s / . , S i r t ~i< 1 ' , 1 t n t 1 c u r t 2 (197:i) 81
4 2 .l H. N < ) o r d ~ k'l'. \L' I I t i n ~ t r ~ t ~ ,in(l l ~ n k.I. (;. M i-d!i (let Llnrlrti, d ( ' o r ) r r l C hem..
2 (1973) 185.
4 3 .l. H. Noorritk a n d P. 'I' Br'urskrsm. .l ( ' r v s l %l01 5irlc(~I..1 ( 1 9 7 1 ) 339.
4.3 ,l. H. F:ric~~~~:irk ~ I I ( ,l.
I A . Ihi,rs, 1 1 1 o f y ( ' / I , , I ~ I . . 7 ( l 9 f i 8 ) 2f;.'j(i.
2 5 D. Mc,ot,. A. t<,~l)<~nt.au. H. Wu~id<.rllch a n d (;. Kost.nati.11r. .I S ~ l t d Stutc C h r m . .
6 ( 1 9 7 3 ) 583.
4 6 R. W. C.; Wvck<)ff.('r\~,slolSlrucliir-es. Vol. I . I n t c r s c ~ r ~ ~Nt3w c e , York, 2nd ed.,
1 9 6 3 , IJ. 337.
4 7 P. W. R. C o r f ~ v l dand H. M. M. St1var1.r. Acla ('rv.~tullogr..2 3 ( 1 9 6 7 ) 156.
4 8 W. C l e ~ g Acts . ('rvslollo~l-..B 3 2 (1 9 7 6 ) 271 2.
4 9 M . Weishaupt a n d .l Stra(.hl<l./ r l ~ ~ t ~ r f o R:jl . ~ w l( 1~9 7 6 ) 5 5 4
50 P. L. Bellon. M. Manasst%r<~ arid M. Sanscln~,KIC Scl., 3 9 ( 1 9 6 9 ) 1 7 3 .
( b ) S. Esprras. Acla ('h6.m Scund.. A30 ( 1 9 7 6 ) 527.
51 P. D. Gdvens. J . .I. Guv. M. .I. Mdvs , ~ n dC;. h1. S h c l d r ~ c k ,jiclo ('rvslullopr.,
B33 ( 1 9 7 7 ) 1 3 7 .
5 2 K. W. Bakrr a n d P. .l. Pauling. J ( ' h c r ~ S<,c.. I)ullor~ 'I'rut~s.,( 1 9 7 2 ) 2264.
5 3 C. .I. Gilmorc a n d 1'. Wc,odward, d. ('hczm Sot , ( ' h ~ m Commut? . . (1971) 1233.
54 .l. J. Guv. P. G. Jnnt.s and Ci. M. S h r l d r ~ c k .lr.lu . Crvstallog~..,8 3 2 ( 1 9 7 6 )
1973
5 5 T. I,. Blundell a n d 11. M. Powc~ll,J C'/~c,ni S ( J ~A. . ( 1 9 7 1 ) 1 6 8 5 .
5 6 K. '4.. I. F. M'rnndn, Aclu Crvslollogr.. 2 3 ( 1 9 6 7 ) 6 4 9 .
57 .l. B. W ~ l f o r dm d 1%.M. Powell. J C'hcm. Soc A , ( 1 9 6 9 ) 8.
5 8 1,. .I. Guggenberger. J Orparlomr~t.Chvrn.. 8 1 ( 1 9 7 4 ) 271.
5 9 V. C;. A n d r ~ a n o v Yu. , 'S. Struchkov and E. K. Itc~sslnskava.J. Chem. Soc.,
C11r.m C u r n m u t ~ . .( 1 9 7 3 ) 338.
6 0 J . A. J . Jarvis, A. Johnson a n d K . .I. Puddephntt. J Chcm. SIIC..Chum. C o m m u n .
( 1 9 7 3 ) 373.
6 1 P. L. Bellon, F. C n r ~ a t i .M. Manassero, I,. Naldml a n d M. Sdnsoni. J Chem. Soc..
Chcjm. C o m m u n . , ( 1 9 7 1 ) 1 4 2 3 .
6 2 P. I,. Bellon. M. Manassero a n d hl. Sansonl, d Chvm. S o c 1)alton 'I'rans.. .
( 1 9 7 3 ) 2423.
6 3 M. F. P e r u t ~a n d U. Welsz. J. Chcw Soc.. ( 1 9 4 6 ) 438.
6 4 A . Rosrnzweil: a n d D. T. Cromer, Acta Cryslullog~. .. 1 2 ( 1 9 5 9 ) 709.
6 5 .l. P. Fackler, Jr., and C. P a p a r ~ / o s ,J. Am. Clif~tfr.Soc., 9 9 ( 1 9 7 7 ) 2363.
6 6 H. M. Colqhoun. T. .J. Greenhough a n d M. G. H. Wallbridge, J Chem. Soc.,
Chrm. Commun., (1976) 1019.
6 7 V. G. Albano. P. L. Bellon. M. Manassero a n d M. Sansoni. J. Chem. Soc., Chem.
Commun., (1970) 1210.

SUBJECT INDEX
Acetate complexes, gold([) '19
Acety iacetonatogoltl c o m p l c x e ~
101, 192
Alhene complexes 148 151
Alkene oxldatlon 256
Alkvlgold(1) complexes 100-102
- , thermal tlc~composrt~on
207
109,
--, vlbratlonal spectra 220- 221
, wlth aclds 11 1
-, wlth acyl ha11dr.s 1 1 2 , 203
, w ~ t halkyl halldrs 2 0 2 2 0 3
, wlth mc,lcur\ (11) hal1dc.5
197-1 9 8
- , wlth metal hallties 1 1 3
Alkyne complexes 148-1 5 1
-, Mossbauer spectra 233
Alkynylgold c ~ > m p l e x r s103- 104
Alloys of gold 6, 164-1 6 5
Alluvlal gold 1
Amhld(,ntate hgands 2 3
Am& complrxes
, gold(1) 51
- gold(1II) 77-78
A m m ~ n emmplexes
-, gold(1) 48
- gold(II1) 77, 1 3 2
-, -, electronlc spectra 239
-, -, vibrational spectra 213,
219
Analysis of gold 243--247
Antihistamine properties 252
Aqueous chemistry of gold 1 8
Aquo comp!exes 1 2 9
-, n.m.r. spectra 225
-, vibrational spectra 217
Arsine complexes
Cat~siunr,cur,~te-(I ) 3b -, vibrational sprctra 221 - 2 2 2
('arbvnc~complexes 144-148 Dialkylgold halides 1 2 6 1 2 7
~u)nicI \ l 4 4 14-5 Dialkylselenide complexes
C a b o n \ Is 1 0 , 4 3 -, gold(1) 6 0
Carboranrb complexes 166-167 -, gold(II1) 8 6
, goltl(l1) 72 Dialkylsulphide complexes
Catalys~s253-256 -, gold(1) 60, 64
Charge transfer spectra 237-239 -, gold(II1) 8 6 , 1 3 2
Chem~lum~nescence246 -, vibrational spectra 217, 219
C h l o r ~ d ec o m p ! ~ x e s 11,2-Diaminoethanecomplexes of
, gold(1) 65 gold(II1) 77
, gold(II1) 9 1 Diazouracil complexes 252
-- , , substltutlon reactions Dibenzylsulphide complexes 6 9 ,
181-184 72
, gold( l ) 5 2 - , stretching force constants -, gold(II1) 1 8 8
- gold(1II) 81, 1 3 4 2 1 1 - 2 1 3 , 218 , n.m.r. spectra 225
A r t h r l t ~ streatment 2 4 8 2 . 5 2 Chlorine wlth gold 3 3 Diethylenctriamine complexes of
Arylgold complexes 1 0 1 Chromatography 243, 247 gold(II1) 7 8 , 1 8 2
, vrbratlonal spectra 221 Chrysotherap) 248- 252 Diethylgold sulphate 1 3 1
, wlth acyl hahdes 1 12 C I D h P effrcts 200 Dimrthylaurate(1) 9 8
.
w ~ t hmetal h a l ~ d e s 114
- -
Cls ~nfluence 216 Dimethylglyoxime complexes
Atomic absorption spectrography "Class b" p r o p e r t l ~ s 22 69, 1 5 7
247 Cluster con?plexes 160- 1 6 4 , Dimethylgold acetate 1 3 0
A t o m ~ cgold 1 0 173-174 Dimc~thylgold(II1)complexes
A u r a t ~ o nr e a c t ~ o n s 1 3 5 - 1 37 , hondlng 163-164 , n.m.r. spectra 223---224
A11de romplc~xrs , preparation 160--l h1 , vibrational spectra 221-222
- gold(1) 49 , structure, 1 6 1 1 6 2 Dimc,thylgold hydroxide 1 3 0
-, n.m.r spectra 2 2 3 Collolds 6 Dimethylsulphoxide complex 8 5
- gold(II1) 123, 1 2 8 Covalency In complexes 25 Discriminating power 182-184
-, - , electronic spectra 239 C y a n ~ d ecomplexes Diselenocarbamate complexes 8 8
A ~ o b e n z e n ecomplexes 79 , gold(1) 45, 256 Disproportionation of gold(1) 22
-
, - , electromc sprctra 239-240 Dithiocarbamate complexes
-, gold(II1) 76, 1 2 9 , 1 8 5 - gold(1) 54, 6 1
Bcnzenethiol reactions 1 9 6 , 201 -, ~nfrarcdspectra 47 - goltl(I1) 5 0
Benzimidazoly lgold complexes Cyanide process 4 - , gold(I11) 69, 8 7 , 1 3 1
105--106 Cyclooctadrcnr complex 1 4 9 Dithiolate complexes 1 2 , 8 7
Riojogical applications 247-253 Cyclopentad~rnvlgoldcomplexes Dithiooxalate complexes 8 5
2,2 -Bipyridine complexes 102, 106-107 Dithiooxamide complexes 85-86
-, gold(1) 4 9 Cyclopropane r s o m e r ~ s a t ~ o2n 5 6 Dithiophosphate complexes 6 2
-, gold(In1) 80, 1 3 3 , 1 8 4 , 191-192 Cysterne complexes 251 Dithiophosphinate complexes 62
2,2 -Blquinolyl complexes 8 0
Bis(dimethy1arsino)benzene Deuterium-hydrogen exchange Electrochemicai analysis 247
complexes 8 4 254 Electron affinity 1 4
Bis(dipheny1phosphino)methane Dialkylaurates( I) 98-100 Electron configuration 24
complexes 73, 1 5 8 , with acids 1 9 6 Electronic spectroscopy 236-240
Bond lengths 261-266 -, with alkyl halides 1 1 8 Electron spin resonance spectra
Borohydrides 30 Dialky lgold(II1) complexes 71
Boron--gold bonds 165-1 6 6 125-1 35 Electrophilic substitution
Bromide complexes -, bonding 1 2 5 reactions 194-199
-, gold(1) 6 5 -, thermal decomposition 207 Enzymes 250-251
-, gold(II1) 9 1
Ferrocenylgold complexes 1 0 6 -, gold(II1) 90 -, stereochemistry 180-181 Penicillamine complex 2 5 3
Fluoride complexes -, Mossbauer spectra 228-234 Linear complexes 1 5 Pentafluorophenylgold complexes
-, gold(II1) 90-91 -, n.q.r. spectra 234 9 9 , 1 2 2 , 135. 1 3 8 . with
--, gold(V) 9 6 - 9 7 -, vibrational spectra 210-21 7 halogens 1 1 5
-, vibrational spectra 2 1 3-214 Halides of gold 31 Maleonitriledithiolate complexes Perchlorate conlplexes, gold(1) 59
Fluorophenylgold complexes Hard and soft acids 22 -, gold(I1) 71 l ,l0-Phenanthroline complexes
-, n.m.r. spectra 226 Hexafluoroaurates(V) 32, 96--97 -, gold(II1) 70, 88-89 -, gold(1) 4 9
Formamidines 1 4 7 Homolytic substitution reactions Manganese-sold bonds 170-1 72, -, gold(II1) 8 0 , 1 3 3 , 1 9 2
Free radical reactions 200-209 200-201 174,176 Phenylgold complexes 107-108,
Hybrid orbitals 1 6 Methyl cyanide complexes 135
G e r m a n ~ u m gold bonds 167-168 Hydrides 30 - , gold(1) 48 -, thermal d e c o m p o s i t ~ o n 1 4 1
Glyoxal p r e p a r a t ~ o n 255-256 Hydridogold(II1) intermediates - , gold(II1) 79
, w ~ t hhalogens 1 15
Gold 196-197 Methylgold(1) complexes 98-100 Phen.{lselenide complex 1 3 1
- , a n t ~ m o n ~ d r10 , Hydrogenation 254 -, photochemistry 11 0
Phenylthioyl rad~cals 200-201
-, n ~ t r ~ d40 e IIydrothermal transfer 2 --,photoelectron spectra 235 Phosphine complexes
, p h o s p h ~ d e 40 , w i t h alkyl halides 1 1 7 -118
Hydroxide complexes, vibrational
--, with alkynes 1 2 0 , gold(1) 5 2
, s e l e n ~ d e 39 spectra 217 , --, bonding 57
-, t e l l u r ~ d e 3, 39 8-Hydroxyquinoline complexes -, with sulphur dioxide 121 , - , p r e p a r a t ~ o n 52, 203-204
Gold(1) 82. 1 3 1 ---,with tetrafluoroethylenr 1 1 9
, -, structure 5 3
- , b r o m ~ d e 31, 36
Methylgold(II1) complc~xes,Imnd , , vibrational spectra 214,
, c h l o r ~ d e31, 33, Immomethy lgold complexes energy 1 4 3
219, 220
-,-, structure 34 105,145 Molecular orhital t h r s r y 2.1
, gold(II1) 8 3 -84, 134
-, c y a n ~ d e 37 I o d ~ d ecomplexes M6ssbaut.r spectra 2 2 6 - ~ 2 3 4
Myocrisin 248
. n.m r spectra 224
- d ~ p h e n y l p h o s p h ~ d5e8 , gold(1) 6 3 Phosphlnc, vhd comolexcs
-, d ~ d 31, e 37 - , gold(II1) 92 - , goltl(1) 99- l 0 0
- , kete,n~dc, 1 0 8 1 0 9 Ionic r a d ~ u s 1 6 , gold(I1) 7 3 , 116, 1 19
, s u l p h ~ d e 38 Ionlsat~onenergles 1 4 -, gold(II1) 1 2 2 , 1 4 3
-, t h ~ o c y a n a t e 37 Ion-selectwe electrodes 247 Photoelectron spectroscopy
Gold(II1) Iron-old bonds 170-173,175 Neutron activation analysis 247 234--235
--, b r o m ~ d e 31, 36 Isocyanate complexes Nitrate complc~xes Phthalocyanine complex gold(I1)
-, c h l o r ~ d e 31, 3 3 -, gold(1) 5 0 -, gold([) 5 9 72
-, -, structure 35 , gold(II1) 1 2 8 , gold(lI1) 8 5 Physical properties of gold 5
-
, , w ~ t halkenes 1 5 0 Isocyan~decomplexes Nobility of gold 18 Piperidinr cornp1t.x 157
, cyanlde 37 , bondlng 45 Nuclear magnetic resonance Porphyrin complex 8 2
-, f l u o r ~ d e31, 32 -, gold(1) 45, 1 1 0 , 144, 1 4 6 , 1 5 7 spc~ctroscopy 223-2 2 6 Potable gold 6
-, fluorosulphate 39 -, gold(II1) 7 6 Nuclear quadrupolc resonance Pourbaix diagram 1 9
- h y d r o x ~ d e 38 Isomerlsation o f hydrocarbons spectroscopy 234 Pseudohalides 37
-, n ~ t r a t e 40 254-255 Purification of gold 5
-, o x ~ d ec h l o r ~ d e38 Isomer s h ~ f t s227-231 Purple of Cassius 7
-, s e l e n ~ d e38 Isotopes of gold 7 Occurrence of gold 1 Pyrazolylgold(1) 51
-, s u l p h ~ d e38 Olefin metathesis 256 Pyridine complexes
Gold(V) Ligand field theory 1 7 Orlho-metallation reactions 1 3 6 , gold(1) 48
-, f l u o r ~ d e 31, 32, 9 6 Ligand substitution reactions Oxidation o f gold(1) 201-203 -, gold(II1) 7 9 , 132, 183-186
Gold coatmg 256-257 -, mechanism for gold(1) Oxidation-reduction potentials , vibrational spectra 219
Gold-gold bonds 157-160 191-194 18 2-Pyridylgold(1) 104, 1 1 0
G r a v ~ m e t r ~analysls
c 244-245 -, mechanism f o r gold(II1) Oxidation states 1 0
179-193 Oxidative addition 1 1 2 , 1 1 6 , 1 1 7 , Quadrupole splittings 231-233
Halide complexes -, role of entering ligand 1 3 7 . ~ 1 3 81, 4 7 , 201-203
-, electronic spectra 236-240 182-185 Oxonium salts 5 8 Radio-isotopes 2 5 3
-, electronic structure 24, -, role of leaving ligand 185-186 Oxygen--donor complexes, Sadiotherapy 2 5 3
236--239 -, solvent effects 1 8 8 gold(1) 5 8 Reactivity o f gold 9
Recovery of gold 4 T h ~ o m a l a t ecomplexes 248-253
Reduction of gold(II1) complexes Th~omorphoim-3-onecomplexes
203-207 204
Reductive elimination 1 1 7 , Thlosulphate complexes, gold(1)
141-143, 1 9 5 , 205-207 58, 1 5 7 , 2 0 5 , 2 4 8
Reef gold 2 Thmurea complexes 2 4 4
Tln--gold bonds 1 6 7 , 1 6 9
Sanocrysln 248 T ~ ~ r ~ m ea nt ra l~bcs ~ s2 1 5
Selenocyanate complexes, gold(1II) T o x l c ~ t y 252-253
128 I'rcn\ effect 26, !88-1 8 9
Sillconrgold bonds 167 fran\ rnflui.nce 26, 214-222, 223
S-methlonlne complex 204 T r a n & h o nmetal-gold bonds
Solgnnol 248 169-176
Solvent extractwn ol gold bonding 176
2 4 8 , 246, 2 17 yrrpdratlon 170- 1 7 4
S p e c t r o p h o t o m r t r ~ canallsls , propr,rt~e\ 1 7 4 - 1 7 5
2i.5 2 16 , structurv 1 7 5 I 7 6
S t a b ~ l i t yof complcxc.~ 22 , v ~ b r a t ~ o nspectra
al 21 1
Stereochem~stry I'rialkylgold(I1I) complexes 1 2 3
- , gold(1) complrxcs l O , rromerisat~on1 3 8 - 1 3 9
- , gold(I1) complc~xes I l , thermal decomposltlon
-, gold(II1) complexcbs 1 2 , 1 X2 205 207
-, gold(V) complcxrs 1 3 , vibr,~tionalspectra 2 2 1
Sterlc ellects 186 - I 8H -, w:th aclds 1 1 0 , 195- 1 9 6
S t ~ h ~ complcxc~s
nr , wgth ha1ogc.n~ 140
, gold(l) 5 2 , w ~ t hmercuryiII) halides lcf7
-, gold(II1) 8 4 , w ~ t hn1trogc.n oxldes 14 1
Succ~nlmidecomplcxcs, goltl(ll1) , wlth sulphur d l o x ~ d e1 4 0
78 Tr~fluoromethylgoldcomplexc~s
Sulphate complexes, golti(1) 5 9 201, 2 0 3
Sulphinate complexcs 1 2 1, 140 Trlmethylsiloxy complex 1 3 0
Sulphite, complexcs 8 5 Trlpvrdzolylborate complextx\
81,190
Tctracyano~.thylt.nccomplt~xcs
119, 151
Vihrational spectroscopy
Tetrahydroalum~nate 30
T r t r a m c t h y l d u r a t ~ 1 2 1 122 210-223
Tetramethy l e t h y l c n t d ~ a r n ~ n r Vinyl acetate manufacture 255
complex 1 9 1 Vinylgold complexes 1 0 7 . 1 5 1
, thermal decomposition 1 4 2
Trtrazolatt, complexes 122
T h ~ o c y a n a t ec o m p l e x t q golti(II1) -, with acids 111
128, 181 1 8 2 -, with mercury(I1) bromide 113
Thioglucosc~c o m p l r x ~ s248 253 Vitamin Blz 9 8
Thiolate complexes
-, gold(1) 61, 62, 64, 248-252 Xanthate complex 1 3 1
-, gold(II1) 1 3 2 X-ray structures 261-266