Polyhedron 52 (2013) 159–164

Contents lists available at SciVerse ScienceDirect

Polyhedron
journal homepage: www.elsevier.com/locate/poly

A general route for the transfer of large, highly-charged polyoxometalates

from aqueous to organic phase
David Gabb a, Chullikkattil P. Pradeep a,b, Thomas Boyd a, Scott G. Mitchell a, Haralampos N. Miras a,
De-Liang Long a, Leroy Cronin a,⇑
a
WestCHEM, School of Chemistry, University of Glasgow, Joseph Black Building, University Avenue, Glasgow G12 8QQ, United Kingdom
b
School of Basic Sciences, Indian Institute of Technology – Mandi, Mandi 175 001, Himachal Pradesh, India

a r t i c l e i n f o a b s t r a c t

Article history:
Available online 23 October 2012
Dedicated to Alfred Werner on the 100th
Anniversary of his Nobel prize in Chemistry
in 1913.
A new mixed solvent procedure which allows the exchange of polyoxometalate (POM) alkali metal cat-
ions for tetrabutylammonium (TBA) and protons is presented. This method has been demonstrated for
simple Keggin [PW12O40]3 and Dawson [P2W18O62]6 POMs as well as the larger phosphotungstates
[NaP5W30O110]14 and [K4P8W48O184]36 for which no TBA salt has been previously reported.
Ó 2012 Elsevier Ltd. All rights reserved.

Keywords:
Polyoxometalates
Ion exchange

1. Introduction
Polyoxometalates (POMs) are a vast and varied class of molecu-
lar metal oxide clusters formed from early transition metals in
their highest oxidation state linked by oxo ligands [1]. These anio-
nic clusters can have nuclearities which range from tens to thou-
sands of atoms [2], and in the solid state they crystallize with
associated cations to balance the negative charge of the metal
oxide cage. When these clusters are reported, often a large amount
of script is committed to discussing the structure of the POM clus-
ter, whilst although the structure-directing role of the cations may
be alluded to, very little time is devoted to a discussion of the cat-
ion composition itself. This is surprising given that the nature of
these cationic species not only controls the solubility of the POM,
but influences its behaviour significantly in solution [3]. POM cat-
ions can be generally split into three classes: (1) inorganic cations
such as alkali metal (AM) ions [4], which allow the dissolution of
POMs in polar protic solvents such as water; (2) organic cations
such as alkylammonium ions (R4N+) [5], which allow the POM clus-
ters to be dissolved in less polar aprotic media such as acetonitrile;
and (3) protons [6], which may enable solubility in both polar and
non-polar solvent.
Previously reported methods allow the interconversion between
the AM salt and the R4N+ salt for smaller POMs such as the Keggin
⇑ Corresponding author.
E-mail address: Lee.Cronin@glasgow.ac.uk (L. Cronin).
URL: http://www.croninlab.com (L. Cronin).
[7], and Dawson [8], anions, [XM12O40]n and [X2M18O62]n respec-
tively, where X is a tetrahedral heteroatom and M is an early
transition metal from which the POM cage is constructed. These
routes generally proceed by dissolution of the AM salt of the POM
in water, followed by the addition of an excess of alkylammonium
salt which causes the aqueous-insoluble R4N+ adduct of the POM
to precipitate from solution. This method may only be successful
if the POM can directly exchange the majority of its AM cations
for alkylammonium cations. However, for large POMs with a
greater charge density it is not possible to directly exchange a
significant number of the AM cations for large organic groups
due to steric factors. In the case of mid-sized POMs it may be
possible to exchange a number of the cations using a phase
transfer reaction [9]. The preparation of POMs as alkylammoni-
um salts is important because it allows the introduction of
POM species to aprotic organic solvents [10], either to react
them further [11], or to perform catalysis on organic substrates
[12]. Such compounds are similarly desirable for analytical
studies such as mass spectrometry [13], and dynamic NMR spec-
troscopy [14], as well as for theoretical investigations of inter-
molecular interactions [15]. Using a two solvent system in this
study, a procedure has been developed which allows for the ex-
change of alkali metal cations on POMs for tetrabutylammonium
(TBA) cations and protons. This has been demonstrated for
the phosphotungstic Keggin ([PW12O40]3 ) and Dawson
([P2W18O62]6 ) clusters as well as the larger Preyssler polyanion
([NaP5W30O110]14 ) [16], and a further giant crown-type poly-
anion ([K4P8W48O184]36 ) [4a].

0277-5387/$ - see front matter Ó 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.poly.2012.10.015
160 D. Gabb et al. / Polyhedron 52 (2013) 159–164

Table 1
Crystallographic data for compounds 1, 3 and 4.

1 3 4
Empirical formula C48H108N3O40PW12 C148H335N11NaO110P5W30 C212H497K4N15O184P8W48
Fw (g mol 1) 3604.54 9722.61 15452.19
Crystal system triclinic monoclinic tetragonal
Space group P1 C2/c I4/m
a (Å) 13.7251(2) 60.6338(19) 28.4263(6)
b (Å) 15.4258(7) 32.0929(10) 28.4263(6)
c (Å) 19.3573(7) 42.8489(9) 33.6681(2)
a (°) 95.346(3) 90.00 90.00
b (°) 93.024(2) 92.155(3) 90.00
c (°) 90.853(2) 90.00 90.00
V (Å3) 4074.0(2) 83 321(4) 27205.7(8)
Z 2 12 2
qcalc (g cm 1) 2.938 2.325 1.886
l (mm 1) 16.965 12.470 19.188
T (K) 150(2) 150(2) 150(2)
No. reflections (measured) 64 449 554 752 21 472
No. reflections (unique) 15 968 71 408 10 233
Rint 0.0683 0.1142 0.0848
Residuals: R1(obs); Rw2(all data) 0.0839; 0.1821 0.1162; 0.2010 0.1095; 0.2209

2. Experimental chemicals and solvents were of analytical grade purchased from

2.1. Materials, methods and instrumentation
K3[a-PW12O40]
nH2O was obtained by addition of a large excess
of KCl to an aqueous solution of phosphotungstic acid with
subsequent recrystallization. K6[a-P2W18O62]
14H2O [4b],
K12
5Na1
5[NaP5W30O110]
15H2O [17], and K28Li5[H7P8W48O184]

92H2O [4a], were synthesized according to the literature. All other
Sigma–Aldrich and used as supplied, without further purification.
Carbon, hydrogen, and nitrogen content were determined by the
microanalysis services within the School of Chemistry, University
of Glasgow using a EA 1110 CHNS, CE-440 Elemental Analyser.
Flame photometric analysis of alkali metal ion content was per-
formed at the Environmental Chemistry Section, School of Chemis-
try, University of Glasgow on a Perkin-Elmer 1100B Atomic
Absorption Spectrophotometer. Thermogravimetric analysis was

Fig. 1. Exchange of polyoxometalate (POM) alkali metal cations for tetrabutylammonium (TBA) and protons in a mixed solvent system (formation of compound 1 is
illustrated above). (a) In the mixed H2O/CH3CN solvent the POM clusters associated with both alkali metal (AM) and TBA cations, and were soluble in the mixture. (b) Upon
acidification with H2SO4 the protonation of the clusters increased, lowering their effective charge, polarity and solubility in water and allowed a sufficient number of the
excess TBA molecules to encapsulate the POM. The adducts retained some CH3CN molecules in their solvation shell and excluded water, leading to the formation of an oil
comprising the POM, TBA cations, protons and CH3CN solvent molecules, whilst the AM cations remained in the mixed solvent phase. (c) Upon removal of the oil layer into
pure H2O, CH3CN leeched out creating a sticky precipitate which was no longer fluid. (d) When most of the CH3CN was washed away the material formed an insoluble powder
in water, which could be crystallized from acetonitrile by ether diffusion. POM anions: green and blue polyhedra; TBA cations: grey sticks; AM cations: dark grey spheres;
protons: light grey spheres. (Colour online.)
 D. Gabb et al. / Polyhedron 52 (2013) 159–164 161

Fig. 2. (a) The arrangement of anions in the extended lattice of compound 3, the TBA salt of the Preyssler POM, as determined crystallographically. Layers of the anion viewed
from above on the left pack in an A–B–A–B fashion, as shown on the right. Although there appears to be empty volume in the crystal lattice depicted on the right, these voids
are presumably occupied by disordered cations and solvent molecules which have not been located crystallographically. (b) The solid state packing in compound 3 is
markedly different from the more regularly oriented arrangement of its potassium analogue depicted on the lower half. The POM clusters are shown as green polyhedra and
all crystallographically-located TBA cations are shown as grey molecules with ball and stick representation. (Color online.)

performed on a TA Q500 instrument under a nitrogen atmosphere.
The heating range was from RT to 1000 °C at 5.00 °C per min. All
FT-IR spectra were recorded on a Shimadzu FT-IR 8400S Fourier
Transformer Infrared Spectrophotometer. Wavenumbers (m ~) are gi-
ven in cm 1; intensities are denoted as wk, weak; sh, sharp; m,
medium; br, broad; s, strong; vs, very strong. UV–Vis spectra of
compounds 1, 2 and 4 were collected using a JASCO V-670 spec-
trometer equipped with an ISV723 60 mm integrating sphere in
diffuse reflectance mode. The spectrum of compound 3 was ob-
tained on a TIDAS 100 diode array fibre optic spectrometer (J&M).
2.2. General synthetic method
The relevant polyoxometalate salt (0.1 mmol) was dissolved in
50 mL of deionized water. Acetonitrile (75 mL) was then added to
this reaction mixture, followed by tetrabutylammonium bromide
(6.0 g, 18.6 mmol). Next, the pH of the solution was lowered to
1.5 using 4.5 M H2SO4, and the reaction mixture set aside. An oily
material began to form and accumulate at the bottom of the flask.
This was transferred by pipette to a centrifuge tube, within which
it was washed several times with water and ethanol, and centri-
fuged to isolate the white powdered product. Crystals of sufficient
quality for single crystal X-ray diffraction were obtained by slow
ether diffusion into an acetonitrile solution of the product.
2.3. (C16H36N)3[PW12O40] (compound 1)
2870 (s, sh), 1950 (w, sh), 1459 (s, sh), 1377 (m, sh), 1070 (s, sh),
968 (s, sh), 884 (s, sh), 748 (s, b), 595 (m, sh), 504 (s, sh). UV-bands,
nm (Abs): 288 (0.77), 350 (0.78).
2.4. (C16H36N)5H[P2W18O62] (compound 2)
Yield = 67%. Elemental analysis for the dried material,
(C16H36N)5H[P2W18O62], C80H181N5O62P2W18, MW = 5576.36 g
mol 1. Anal. Calc.: C, 19.79; H, 3.74; N, 1.44. Found: C, 19.72; H,
3.67; N, 1.49%. TGA stepped weight loss to 1000 °C, Calc.: 24.97.
Found: 26.8%. Characteristic FT-IR-bands: 3444 (b, s), 2924
(s, sh), 2920 (s, sh), 2865 (s, sh), 1903 (w, sh) 1626 (m, sh), 1459
(s, sh), 1378 (s, sh), 1131 (m, sh), 1082 (s, sh), 997 (m, sh),
923 (s, sh), 772 (s, br), 521 (s, sh). UV-bands, nm (Abs): 350 (0.85).
2.5. (C16H36N)9H5[NaP5W30O110] (compound 3)
Yield = 40%. Elemental analysis for the dried material,
(C16H36N)9H5[NaP5W30O110], C144H329N9NaO110P5W30, MW =
9157.53 g mol 1. Anal. Calc.: C, 18.16; H, 3.48; N, 1.32; Na, 0.24.
Found: C, 17.73; H, 3.41; N, 1.37; Na, 0.21%. TGA stepped
weight loss to 1000 °C, Calc.: 22.90. Found 25.2%. Characteristic
FT-IR-bands: 3497 (b, s), 2965 (b, vs), 2901 (b, vs), 1632 (s, sh),
1488 (vs sh), 1411 (s, sh), 1176 (vs sh), 1085 (vs sh), 949 (b, vs),
734 (b, vs), 540 (s, sh), 411 (b, vs). UV-bands, nm (Abs): 210
(0.48), 286 (0.14).

Yield = 58%. Elemental analysis for the dried material,
(C16H36N)3[PW12O40], C48H108N3O40PW12, MW = 3604.42 g mol 1.
Anal. Calc.: C, 15.98; H, 3.02; N, 1.17. Found: C, 15.95; H, 2.93; N,
1.18%. TGA stepped weight loss to 1000 °C, Calc.: 20.17. Found:
21.8%. Characteristic FT-IR-bands: 3404 (m, br), 2953 (s, sh),
2.6. (C16H36N)13H23[K4P8W48O184]
2CH3CN (compound 4)
Yield = 50%. Elemental analysis for the partially dried material,
(C16H36N)13H23[K4P8W48O184]
2CH3CN, C212H497K4N15O184P8W48,
MW = 15431.29 g mol 1. Anal. Calc.: K, 1.01; C, 16.49; H, 3.25; N,
162 D. Gabb et al. / Polyhedron 52 (2013) 159–164

1.36. Found: K, 0.99; C, 16.79; H, 3.36; N, 1.32%. TGA stepped
weight loss to 1000 °C, Calc.: 21.05. Found: 26.6%. Characteristic
FT-IR-bands: 3356 (s, br), 2951 (s, sh), 2865 (s, sh), 2090 (w, br),
1628 (m, sh), 1463 (s, sh), 1377 (m, sh), 1132 (s, sh), 1074 (s, sh), 685
(s, br), 355.8 (s, sh). UV-bands solid state, nm (Abs): 356 (0.85).
2.7. Single-crystal structure determination
Suitable single crystals of compounds 1, 3 and 4 were selected
and mounted onto the end of a thin glass fibre using Fomblin oil.
X-ray diffraction intensity data was measured on an Oxford Dif-
fraction Gemini Ultra with an ATLAS CCD detector [1, 3: k(Mo
Ka) = 0.71073 Å; 4: k(Cu Ka) = 1.54184 Å] at 150(2) K. Data reduc-
tion was performed using the CrysAlisPro software package and
structure solution and refinements were carried out using SHELXS-
97 [18] and SHELXL-97 [19] via WinGX [20]. Corrections for incident
and diffracted beam absorption effects were applied using analyt-
ical numeric absorption correction using a multifaceted crystal
model [21]. Structures were solved by a combination of direct
methods and difference Fourier syntheses and refined against F2
by the full-matrix least-squares technique. The W, P and O atom
positions are crystallographically well-defined, but the solvent
molecules and cations, because of disorder, are difficult to fully
analyse by crystallography alone. Therefore, the final molecular
formula has been determined by a combination of elemental anal-
ysis, thermogravimetric analysis and crystallography. Due to the
nature of the crystals obtained by diethyl ether diffusion into ace-
tonitrile, the quality of the reflections from the single crystals were
not of very good quality. We attempted to collect as many reflec-
tions as possible; however, the resulting data are still relatively
weak. The crystallographic data for compound 2 was reported pre-
viously by our group [8a]. Crystal data, data collection parameters
and refinement statistics for 1, 3 and 4 are listed in Table 1.
3. Results and discussion
3.1. Synthesis of (C16H36N)3[PW12O40] (1), (C16H36N)5H[P2W18O62] (2),
(C16H36N)9H5[NaP5W30O110] (3) and (C16H36N)13H23[K4P8W48O184]

2CH3CN (4)
In step one of the procedure (Fig. 1a), the as-synthesized alkali
metal salt of the POM (0.1 mmol) was dissolved in 50 mL of water
before the addition of 75 mL of acetonitrile, followed by a large ex-
cess of TBA to give a lightly-coloured, cloudy solution. This solution
was then acidified to pH 1.5 using 4.5 M H2SO4 which increased the
turbidity of the solution and resulted in the spontaneous formation
of oil droplets containing the POM associated with both TBA ca-
tions and protons (Fig. 1b). Some acetonitrile molecules remained
within this third phase allowing the assembly to retain a fluid con-
stitution. After separating the two layers by pipette, the oil was
then centrifuged and washed with deionized water. This step pro-
moted leeching of acetonitrile from the oil and resulted in the for-
mation of a sticky white precipitate (Fig. 1c). Again, the two layers
were separated by pipette and further centrifugation before this
time washing the remaining solid consecutively with water and
absolute ethanol. The product remained as a white powder upon
drying (Fig. 1d). Crystals of compounds 1–4 were obtained by
dissolution of 0.2 g of the powder in acetonitrile, followed by slow

Fig. 3. (a) The solid state packing of polyanions in compound 4, the TBA salt of [K4P8W48O184]36 . As in compound 3, the POM units stack in an A–B–A–B fashion. (b) The
packing of the previously reported mixed potassium/lithium salt of [K4P8W48O184]36 is shown on the bottom. Although the POM clusters are arranged in the same manner
in both instances, from a comparison of the two crystal structures it can be seen that the space between the polyanions is significantly larger in the TBA salt. This may be
attributed to the much larger size of the TBA cations when compared to the alkali metals.
 D. Gabb et al. / Polyhedron 52 (2013) 159–164
diffusion of diethyl ether into this solution. The formula of the
synthesized salts as determined by a combination of single crystal
X-ray diffraction, CHN microanalysis, flame photometry and ther-
mogravimetric analysis are (C16H36N)3[PW12O40] (1, 0.19 g, 58%),
(C16H36N)5H[P2W18O62] (2, 0.17 g, 67%), (C16H36N)9H5[NaP5W30O110]
(3, 0.17 g, 40%), and (C16H36N)13H23K4P8W48O184
2CH3CN (4,
0.12 g, 50%). Compounds 1 and 2 have been previously reported
[7b,8a], but are presented here to illustrate the generality of this
new synthetic procedure. The polyanion in compound 3 has been
reported as a TBA salt with a complexed Eu(III) cation in the mole-
cular cavity [22], but no crystal structure has ever been reported.
This Preyssler anion has also been reported as a tetraheptylammo-
nium (THA) salt [23]. Compound 4 has not been previously
reported and represents the first successful preparation of an
organic-soluble salt of [K4P8W48O184]36 , a high nuclearity
polyanion with significant charge.
3.2. Structural analysis of (C16H36N)9H5[NaP5W30O110] (3) and
(C16H36N)13H23[K4P8W48O184]
2CH3CN (4)
Considering more closely the two novel compounds, 3 retains a
Na+ cation within its central cavity, but the external AM cations are
all replaced by TBA and protons. Similarly, compound 4 retains
four K+ cations within its central cavity (disordered over eight
hinge positions with half-occupancy in each location). It was previ-
ously thought that these cations were integral to the stability of
the [P8W48O184]40 ring, although a recently published paper
shows that it is possible to make an analogue containing the sim-
ilarly-sized ammonium cation in place of potassium [24]. In both 3
and 4, there is clearly insufficient space within the cavity to replace
the AM cations with TBA and sufficiently counter the repulsions of
the exposed oxygen surfaces of the inner rings.
The packing of compound 3 in the solid state is somewhat dif-
ferent to its potassium analogue (Fig. 2), presumably due to the
major differences in both the size of the cations and their nature,
as well as the degree of solvent incorporated. The solid state struc-
ture of 4 more closely resembles that of its corresponding mixed
potassium/lithium salt (Fig. 3), except that there is greater spacing
between the clusters to accommodate the larger TBA cations.
Unfortunately, not all of the TBA cations may be located by crystal-
lography. This is due in part to the quality of the crystals obtained,
but also due to the nature of the TBA cations, whose long and flex-
ible alkyl arms can be found in a range of locations, ensuring weak
diffraction spot intensity. Therefore, the formulae for compounds 3
and 4 are based on a combination of crystallography, elemental
analysis and thermogravimetric methods.
4. Conclusions
Using this mixed solvent method, all of the AM cations associ-
ated with the native salts of [PW12O40]3 and [P2W18O62]6 have
been exchanged for TBA (there is also one proton found in com-
pound 2). This is possible due to the charge density on the polyan-
ions being low enough to accommodate the required number of
TBA molecules around the cluster to balance the negative charge
of the POM. Whilst all of the external cations associated with the
crown-type polyanions [NaP5W30O110]14 and [K4P8W48O184]36
were exchanged for TBA, both still contain some AM cations
within their cavities, as well as many additional protons. These
protons help to balance the higher charge associated with larger
POMs, whilst occupying very little volume in comparison to TBA.
Therefore, strongly acidic conditions are required to mediate the
exchange of AM cations for TBA associated with larger POMs. An
oily interface forms spontaneously from a mixed solvent solution
of POM, AM cations and an excess of TBA cations at low pH.
163
In summary, a new synthetic procedure has been devised which
allows the straightforward exchange of polyoxometalate AM cat-
ions for TBA. This high yielding, general method allows the effec-
tive transfer of POMs from water to less polar solutions. The
exchange of all AM cations for TBA in compounds 1 and 2 demon-
strates the facile nature of cation exchange in smaller POMs, in
which the charge density is low enough to allow coordination so-
lely with bulky R4N+ cations. However, the greatest advantage of
this new procedure is that it allows the partial exchange of AM
cations of large POMs with high charge densities, such as in com-
pounds 3 and 4. Enabling organic solubilization of these com-
pounds opens up many avenues for future research, including
their reaction in non-polar solvents with organic linking species
and the investigation of the catalytic behaviour of such compounds
towards organic substrates in non-aqueous solvent. Further studies
by our group will investigate the nature of the oil formed during
the cation exchange, and look to capitalize on the pathways
opened up by this method towards mass spectroscopic analysis
and the observation of dynamic processes by low-temperature
NMR.
Acknowledgements
This work was supported by the EPSRC, the Leverhulme Trust,
WestCHEM, the Royal Society/Wolfson Foundation, and the Univer-
sity of Glasgow. We thank Michael Beglan for assistance with flame
photometry.
Appendix A. Supplementary data
CCDC 891265–891267 contain the supplementary crystallo-
graphic data for 1, 3, and 4. These data can be obtained free of
charge via http://www.ccdc.cam.ac.uk/conts/retrieving.html, or
from the Cambridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK; fax: (+44) 1223-336-033; or e-mail:
deposit@ccdc.cam.ac.uk. Supplementary data associated with this
article can be found, in the online version, at http://dx.doi.org/
10.1016/j.poly.2012.10.015.
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