Resource Papers-I
-
F. Albert Cotton
Massachusetts Institute of Technology
Cambridge, Mass.
Ligand Field Theory
The presentation of ligand field theory in
the first college ehemistry course cannot be said to be
essential. If time is limited, or if the ability of the
students and/or their interest in chemistry as a pure
science rather than as a branch of useful knowledge are
not well above average, I believe there are many other
topics which can be more profitably discussed. There
is time enough in later years of the chemistry cur-
riculum for those who do elect chemistry as a major
subject to tackle this aspect of it. However, in a
thorough sort of course, taught to a select, science-
oriented group of students, the subject of ligand field
theory might form an interesting and stimulating part.
Certainly it is an important part of the "vocabulary"
of modern theory which teachers should know so that
their presentation not be erroneously simplified a t any
level. I t is important, however, to present it in such
a way as to avoid creating false impressions about
the nature of ligand-to-metal bonds; this requires of the
teacher, first, an awareness and understanding of the
dangers and, sewnd, the possession of some concrete
ideas about how to avoid them. This article presents
an outline of ligand field theory in its present state and
a t an introductory level; it suggests, partly in precept
and partly in example, a presentation of this subject
which is primarily intended to be appropriate in the
general chemistry course, but it also raises some points
which will be of wncern to those introducing ligand
field theory to students at any level.
Ligand field theory can be defined as the theory of (1)
the origins and (2) the consequences of the splitting of
inner orbitals of ions by their surroundings in chemical
compounds. In this article we shall restrict attention
primarily to penultimate d orbitals, i.e., the 3d orbitals
for ions of the first transition series, 4d and 5d orbitals
for ions of the sewnd and third transition series. To a
considerable degree, it is possible to deal with the two
parts of ligand field theory separately; this has the im-
portant consequence that many of the significant and
relatively straightforward results of d-arbital splittings,
e.g., ligand field stabilization energies, stereochemical
preferences and, of course, spectroscopic and magnetic
behavior, can be discussed pragmatically without neces-
sarily going very far into the inherently &&cult and
tedious question of what causes the splittings. Of
course, a truly rigorous discurnion of all the wnse-
quenoes of inner orbital splittimgs could not be given
without intimately interweaving an examination of the
466 / Journol of Chemical Education
Prepored under the sponsorship of
The Advisory Council on College Chemistry
causes, but for most undergraduate courseeand cer-
tainly for the introductory course--such rigor and wm-
prehensiveness are unnecessary.
Causes of Inner Orbital Spitting$
The possibility that the degeneracy of atomic orbitals
will be sigxZ6oantly split when an ion is placed in a
chemical environment was fist suggested by Bec-
querel (1) and the problem was then examined in con-
siderable detail by Bethe (2). Bethe's work consists
of two parts: first, in one of the earliest applications of
symmetry arguments to a chemical problem, Bethe
determined the qualitative nature of the orbital split-
tings for various important geometries. These quali-
tative results are correct whatever the mechanism
(electrostatic, or covalent, as discussed presently)
which brings them about. For d orbitals, in several
important geometrical situations, they are as follows:
In both octahedral and tetrahedral surroundings, the dw,
d, and dvz orbitals remain equivalent, as do d ~ * - and~ %dis
orbit&.
In square surroundings, the drz and 6.orbitale remain equiva-
imr, but the d,,, d,,-,I and d.1 orb~talssrenot equivalent toany
othem.
Bethe obtained these and other results by formal,
group-theoretical methods, but they can also be ob-
tained, or at least their correctness strongly suggested,
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Penna. 19104, ia the chairman.
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Jozmml of Chemieol Educatiun.
by informal, pictorial arguments, requiriig only the Similarly, for a tetrahedral set of four ligands, ar-
common sense' any bright freshman should have. To ranged as shown in Figure 4 a t alternate vertices of a
do so, it is first necessary to present pictures showing cube,a it can be seen that the d,,, d,,, and d,, orbitals
the shapes of the usual five d orbitals, Figure 1. In stand in one sort of relationship to the ligands, namely,
addition, it should be pointed out that the d.. orbital with their lobes pointing to cube edges, while the
can be regarded as a combination, in equal parts, of two
orbitals, dZ2-., and d..-,., each of which is shaped l i e
the other four d orbitals; this is illustrated in Figure 2.%
It is now supposed that the metal ion is placed in an
octahedral array of six ligands, as shown in Figure 3.

Figure 3. The arrangement of the sir ligmd d m r in an octohedrd com-

plex in relation to the some Cortesion coordinate system ured in Figures 1
and 2 forthe d orbit&,

Figwe 1. Balloon pictures of the conventiomol set of d orbitals. The sur-

facer are drawn to enclose o mojor p o r h o y , roughly, 90%-0f the
amplitude of the wave functions. The sign of the wove functions h each
lobe is shown. Since the distribution of electron density ir given by @, it
will in each core be quite similar to the shape of the wave functions d the
orbitals.

Figure 4. The arrangement of tho four ligand atoms in a tetrhoedrd com-

plex in relation to the some Cartesian coordinate system ured in Figurer 1
ond 2. Note how the tetrahedron i s composed of four alternate corners of
a cube.

d ~ ~ z ~ 2 . ~ 2 iz2
Figure 2. Drawings showing how the d'z orbit01 consids of o ond
o d.2-,r orbital in equal proportions.

It should not be hard to see that the d,~-,., d+,,, and

d.,-,. orbitals are all oriented in one way in relation
to the six ligands, while the d,,, d,,, and d,, orbitals
are all oriented in a second way. Specifically, all those
in the first set have each of their lobes going toward a
ligand atom, while each one in the second set has each
lobe going between ligands. Thus, we get the result
mentioned above that the d,,, d,,, and d,, orbitals are
equivalent to one another, whereas the d+,. and d,. Figure 5. The arrangement of four ligand atoms in a rqumre complex in
(being made up of equal parts of the equivalent pair relation to the some Cartesian coordinate system "red in Figurer 1 and 2.
dE2-,,, ds2-u2) are different from the first three, but
equivalent to one another. d,.-,., d+,., and d..-,. orbitals stand in another re-
lationship; namely, their lobes point to the centers
Sameone is supposed to have remarked that "group theory of cube faces. Hence, again, we conclude that d,,,
is just araaniaed
- common sense." which is not too m - a t an
exaggeration. d,,, d,, form one equivalent set while d,.-,a and dB.form
For algebraic details, see COTTON ANn WILKIN~ON, page a second equivalent set.
973. It is necessary to make this breakdown of the dal orb~tal Finally, it can be seen that the d,, and d,, orbitals
in order to demonstrate by the pictorial argument that drg and both have the same relationship to the ligands set a t the
d.z-,x are not only different from the other three, but also are comers of a square in Figure 5, that both d+. and
epuivaht to ae another. It, is to be stressed, however, that the
dat-.* and d.r-,. orbit& have no a d d existencealong with the
other four, since there can be only five independent nd wave The usefulness of this way of looking at a tetrahedron, for
functions. many purposes besida the present one, is worth emphasizing.

Volume 41, Number 9, September 1964 / 467

d82-,2 have a second relationship to the ligands and
that each of the two remaining orbitals is related in
still diierent ways.
The question now arises as to how much the energies
of the nonequivalent orbitals, or sets of orbitals, may
differ. It must be assumed that if two orhitals, even
if intrinsically similar, are diierently oriented toward
their surroundings, there will, in principle, be some
difference in the energy of an electron depending on
which of them it occupies.
The second part of Bethe's paper offereda n answer to
this question based on the assumption that the ligands
can be treated as point negative charges, a model which
has often been considered to represent the chemist's
concept of purely ionic bonding. (In fact, it does not,
as will be seen.) Using this model, it is easy to see that
qualitatively, a n electron in an orbital whose lohes
point a t the negatively charged ligands will have a
higher electrostatic potential energy than an electron
in an orbital whose lobes point between ligands. I n
other words, the former orbital is a less stable one and
lies higher on an energy level diagram of the usual type
than does the latter orbital. Figure 6 illustrates these
results for the octahedral, tetrahedral and planar cases.
It should be noted that for the souare environment. the
ordering of the orbitals is not e x h y fixed by the sym-
metry alone, but depends in certain respects (e.g., as to
whether the d,, orbital lies above or below the d,,
orbital) on the physical details. The arrangement
shown in Figure 6 is the one believed to be correct in
most real cases. More generally, the relative stabiilities
of a series of inherently similar orbitals will vary in-
versely according to the extent to which they bring
the electron into proximity with the negative ligands.
The argument may be generalized to include not only
negatively charged ligands, but dipolar ones, which will
he so oriented as to have their negative ends closer
than their positive ends to the metal ion. Bethe
showed further that the actual magnitudes of the
energy differences (e.g., AO and A , in Figure 6) can be
calculated using this electrostatic model if one can
select the proper magnitudes for the metal-ligand dis-
tance, and the ligand charge (or dipole moment) and
assign an appropriate radial part4 t~ the wave function
for the d orbitals. I n relatively recent times, Ball-
hausen (5) showed that if these parameters are assumed
to have the same values in an octahedral complex,
MX6 and a corresponding tetrahedral one, MX,,
the ratio of A , to A. will be v9. It has also been shown
that the absolute values of A. (or A 3 can be obtained
withm a factor of less than two by choosing reasonable
values for the various parameters required.
However, in spite of all this sort of pragmatic success,
this electrostatic model is now known to be unrealistic
and ultimately unsatisfactory. It has been discredited
both experimentally and theoretically. The experi-
mental evidence against it comes from a variety of
sources all showing that electrons which are supposed
to be entirely in the metal ion d orbitals, according to
'When an orbital wave function is expressed in sphericd
coordinatee $(7, a, 9) = R(r)B(B)@(4), the radial part is the I2(r).
The parameter r measurea the radial distance from the origin.
The angulss psst of the wave function is B(B)*(+)which involvea
the direction in space from the origin and depends only upon the
angles 8 and 4.
468 / Journal of Chemicol Education
Bethe's point charge model, actually spend a part of
their existence in orbitals "belonging" to the ligand
atoms? Such results imply that there is covalence in
the metal-ligand bonding; some of the data permit
quantitative estimation of the amount of covalence.
From the theoretical side, the inadequacy of the
point charge model (as other than a physically mean-
ingless formalism leading to useful equations) may be
described as follows (4). First, let us recognize that the
ligand atom is not a point. It is an object of about the
same size as the metal ion and it is built in the same
way. An F- ion, for example, consists of a positive
nucleus of charge +9e, which is essatially a point,
surrounded by a spherical cloud of total charge 10e, -
about 90% of which lies within a sphere whose radius
is about equal to half the M-F distance in an MF.
complex ion or in a MF, salt.
Ociohedral Tetrohedrol Square
Figure 6.Orbital rpliwing diagrams for the Ihree most important types of
complex. Orbitals within each pair of bracer are of identical stobilily.
The point charge model does not meaningfully
correspond to the concept of ionic bonding because a
point charge does not meaningfully represent the
way one ion "looks" to the outer electrons on another
ion which is within about two A of it.6 However, a
reasonable representation of a purely electrostatic
interaction between the d electrons of a cation and an
anion, is that given in Figure 7, where the anion is shown
as an entity with structure and finite size, as described
above. Using this qualitatively realistic representa-
tion of the physical situation, the following argument
may be developed.
The evidence will not be reviewed here. Several snmmeries
are cited in the bibliogmphy. Those in ORGEL,BALLHAUSEN,
and C o m AND ~ WILKINSON me especirtlly recommended.
0 To more deeply buried eleotrons of a cation, a near neighbor
anion may come closer to appearing as a point negative oharge.
Recall in this connection s, basic theorem of eleotrosts.tim, due to
Gauss, which st&^ that if a tmt charge lies completely outside
of any charged sphere, it experiences the same force as it would
if all the charge on or in the sphere were concentrated in a point
at the center of the sphere. For the r a n earth ions, calcula-
tions of orbital splittings using the paint charge model may there-
fore have somewhat more physical meaning, although there is
evidence (6) to show that here, too, covalence playa a role. The
one important situation that comes to mind in which the point
dipole model for the surroundings of a cation may be physically
realistic is in the eomputatian of the electrostatic effect produced
by an array of ions in a crystal which lie outside of the firat co-
ordination shell of the cation being treated. Even for second
nearest neighbors, however, some significant covalence effect,
or orbital werlap, evidently occurs as shown by the existence of
a contact shift (6) in the nuclear resonance frequency of I7O in
the ion pair or "outer sphere complex!'
 An electron occupying a n orbital which has lobes
such as A and A' in Figure 7, directed a t the ligand
atoms will feel the positive charge of the nucleus (or the
net positive charge of the compact core, in a heavier
atom) rather strongly, thus off-setting appreciably
the repulsive effect it feels from the diffuse electron
cloud into which it penetrates. On the other band,
Figure 7. A drawing of port of o complex showing two lobes, A, A' of an
eo type metal orbital, two lobes, B, B' of ah. type metal orbital and two
ligond abms. The spheres enclosing mart of the electron clouds of the lig-
and clouds of the ligond otomr ore also shown.
an electron occupying an orbital which has lobes, such
as B and B' in Figure 7, directed between ligand atoms
feels the repulsive effect of the electron cloud nearly
as much as the electron in A, but feels the counter-
vailing effect of the nucleus less. Thus, instead of
concluding that the electron must be much more stable
in orbital B than in A, as we do in the point charge
model, we conclude that the stability difference will
be either only slightly in favor of B, or possibly, even
slightly in favor of orbital A . Actual calculations, using
realistic ( e . , Hartree-Fock) orbitals for metal and
ligand atoms have shown this to be true quantitatively
(4).Thus, if we take a realistic model of the ligand
and consider only electrostatic metal-ligand inter-
actions (that is, assume a model which realistically
represents "ionic bonding") we cannot explain the
observed splittings of d orbitals.
It has been shown, however, that when the effects
of covalent bonding are introduced, they give a splitting
which is qualitatively correct and, if sufficiently elabo-
rate calculations are made (very elaborate, unfor-
tunately), almost quantitatively correct results can
be obtained (7).
It is not very difticult to see, a t least qualitatively,
that covalent bonding will operate in this way. When
each of two atoms has an orbital directed toward the
other one (ax, a2, Fig. 8a), and these atoms approach
to withim a few Angstroms of one another, the orbitals
become mixed to form two new orbitals, one, (as),
having relatively high amplitude (high electron con-
centration) between the two nuclei and the other, ( a d ,
having relatively low amplitude (low electron concentr&
tion) between the nuclei. When electrons occupy
the first, (a bonding orbital), the atoms become bound
together, while when electrons occupy the second,
(an antibondimg orbital) a repulsive or antibonding
force is set up. Furthermore, if the two atomic
orbitals with which we begin have rather different
energies, the resulting bonding orbital will have pre-
dominantly the characteristics of the lower energy
atomic orbital, while the resulting antibonding orbital
will have predominantly the characteristics of the higher
energy atomic orbital: this is represented in Figure
86. However, if the two atomic orbitals (a, r in
Fig. 9) are of such a nature that they have no net
overlap, there is no mixing and no formation of bonding
and antibonding orbitals.
Now the relationship shown in Figure 8 is that be-
tween the e, orbitals' of a metal ion and the a orbitals of
ligand atoms, while the relationship shown in Figure 9
is that between the tt, orbitals of a metal ion and the
a orbitals of ligand atoms. The complete result, a
combination and elaboration of Figures 8b and 9b
is shown in Figure 10.
(01 (bl
Figure 8. Sketch showing the formation of bonding ond ontibonding
type orbitals, ruch or thore formed b y overlap of metal en orbitals with
oppmpriote ligond orbitals in octahedral mmplexes.
(01 (bl
Figure 9. Sketch showing the lack of interaction between o o orbit01 (ruch
as o Isorbital of a metol ion1 ond a ligand *orbital.
Figure 10. Energy level diagram showing the results of 011 the interactions
between the o orbitalr d a ligond and the h. and en orbitalr of a metol
10".
Now it can be seen that by considering the overlap
of orbitals, we have arrived a t the same qualitative
result as that given by the point charge electrostatic
model: the fivefold degeneracy of the d orbitals is
split in an octahedral environment, so that the e,
orbitals become less stable than the h, orbitals. For
all of the principal chemical consequences of orbital
splittings, if is only necessary to know the correct
ordering of the orbitals; the actual magnitude of the
'The symbolism here adopted is that now most generally
accepted. Readers need not worry about its full implications
which derive from the use of Mullikan symbok and character
tables to describe molecular symmetry. The e implies s. two-
dimensional representation, t, a. three-dimensional represent%-
tion; g (from the German gerade, meaning even) implies even
symmetry with respect to inversion. (See COTTON, F. A,,
"Chemical Applications of Group Theory," p. 72.)
Volume 41, Number 9, September 1964 / 469
splitting, AO or A,, can be left as a parameter to be electrons in e, orbitals, rather than bo orbitals, is
determined in some one experiment and the results of 2 A or the low-spin confignration in which the energy
other experiments then predicted. Thus, while the 2P is expended to pair up electrons. Again, the crite-
point charge model is physically without meaning, it rion which determines the preferred arrangement is
does give results which are in general qualitatively simply whether P or A is the smaller quantity. These
correct. It can therefore be considered as a useful results, as well as those obtained analogously for the
mathematical model, but it should not be taught as in d6 and 8 cases are illustrated in Figure 11.
any sense a physical model.
Some Consequences of Inner Orbital Splittings
When the degeneracy of a set of orbitals is split,
electrons no longer will occupy all members of the set
with equal probability. Instead, they tend to occupy
the more stable ones preferentially, subject to restric-
tions arisiig from Pauli's exclusion principle and from
interelectronic repulsions. The former require no High-spin Low-spin High-spin Low-soin
special discussion; they are the same as for free atoms
and ions. For present purposes, the phenomenon of
- - -
Sfdcs
Slates
-,- gE?.?- States
- 4
-
-
interelectronic repulsion-which results from both d4 d5
simple coulombic repulsion and from exchange energy
variationecan be expressed as follows: the placing
of a second electron in an orbital already occupied
by one electron, instead of in an equivalent, but un-
occupied orbital, requires the expenditure of an in-
terelectronic repulsion energy, or pairing energy, P,
which, to a reasonable approximation, may be con-
sidered a constant for all of the nd orbitals of a given
ion. With only these simple considerations, it is
possible to forecast accurately the way, or the two
possible ways, in which the electrons will be distri-
buted amongst the d orbitals of au ion in an octahedral
ligand field for any case from d1 to de. Similar ar-
guments can be devised for cases where the ligands are
differently arranged, e.g., tetrahedrally, or in a square.
For a dl ion, the single electron naturally goes into
Figure 11. Diagrams shoving the most stable orrangernenk of electrons in
one of the b , orbitals, and the ion can be said to have a the d orbitals of ions in octahedral complexes.
kr configuration. Similarly, d 2 and da ions will have
bo2and boa configurations, with each electron in a For a d8 ion, it is impossible to have fewer than three
different k , orbital and all electron spins parallel electron pairs, and the configuration having the greatest
(Hund's rule8), as shown in Figure I l a . For a d 4 ion, number of b , electrons, b,6e02,must be the most stable.
there are two possibilities. All electrons may occupy Similarly, for a de ion, the most stable arrangement
the bs orbitals (k,') but then one orbital must be must be tP,6e,3. By exactly similar arguments, the
doubly occupied and the stability of the confignration results for tetrahedral complexes can be obtained.
is lessened by the pairing energy, P. Alternatively, (Kote, by reference to Figure 6, that in this case, the
we may have the configuration t2,8e, which does not e, orbitals are lower in energy than the bg orbitals.)
require expenditure of pairing energy, but does re- However, so far as is known a t p r e s e n t a n d few if
quire expenditure of the energy A to elevate one of the any exceptions are ever likely to be discovered-there
electrons to the unstable e orbital. The configuration are no low-spin tetrahedral complexes. This is be-
which is actually adopted in a given case is deter- cause tetrahedral splittings A , are too small to exceed
mined by which of these energies is the smaller: if P. Therefore, the only important results for the
A < P we have kgse,and if A > P we have kg4. The various d" ions in tetrahedral complexes are the fol-
&,Qe, configuration has four unpaired electron spins, lowing high-spin configurations:
while kO4 has only two unpaired electron spins. Accord-
ingly, the former is called the high-spin configuration
and the latter the low-spin configuration.
For a d5 ion we may have the high-spin t2,ae,%on-
figuration, in which the total energy expended to put The purely theoretical possibility of a low-spin con-
Hund's rule, originally establishedfrom spectroscopicstudies,
figuration does exist, however, for the d 3 4 cases.
states that the lowest of several posaible energy states for a free It is to be noted that these results were obtained
atom or ion will be that with "maximum multiplicity." The without any knowledge of the actual cause of the
multiplicity is defined as 2S+1 where S = Zsr, the spin vectors splitting or any specification of the energies of the &
of the electrons occupying the equivalent orhitah. In effect, and e orbitals relative to any reference energy what-
it m e m that electrons spread out aver a set of equivalent orbitals
with their spins para11el to the maximum possible extent. See, for ever. With these configurations as a basis, i t is
example, HERZBERQ, G., "Atomic Spectra and Atomic Struc- possible now to examine some of the important con-
ture," Prentice-Hall, Inc., New York, 1937, p. 135. sequences of the d orbital splitting.

470 / Journal o f Chemical Education

Magnetic Properties
In order to predict or explain magnetic properties
of a transition metal ion in its complexes or other
compounds, our first need is always to know how many
unpaired electron spins it has or may have. The d i 5
cussion may then proceed to higher levels of sophistica-
tion if desired, hut this basic question of how many
unpaired electrons there are must always be answered
first.
By referring to the electron coniiguration diagrams
in Figure 11, we see first of all that for dl, d2, da, d3,
and d9 ions in octahedral environments, there will
always be 1,2,3,2,or 1 unpaired electrons, respectively,
no matter how great the value of AO may b e ~ o m e . ~
Deviations from these numbers in the dZ, d3 or d8
cases (provided i t is certain they are not due to any
intermolecular etrects) can he taken to indicate that
the environment of the ion actually departs appreciably
from the octahedral arrangement.
For d4, dd d6, and d' ions, the number of unpaired
electrons can be either the high-spin ones, 4,5,4,3 re-
spectively, or the low-spin ones, 2, 1, 0, 1 respectively,
depending on the magnitude of & relative to P for
the ion in question. Now the value of P for a given
ion can be evaluated fairly reliably from data on the
spectrum of the gaseous ion; P values are, with few
exceptions, known quantities. Therefore, for a series
of complexes of a given ion, some high-spin and some
low-spin, we can draw the conclusion that all ligands
giving the low-spin configuration produce A values in
excess of P, while all ligands giving the high-spin con-
figuration, produce A values less than P. From the
spectrum of an ion in a given complex, the actual value
of A can be determined (see below). It has been
found, without exception, that predictions of the kind
just described are correct. For instance, for the d"
configuration of Coa+,data from spectra of the gaseous
ion lead to a value of about 50 kcal/mole for the pairing
energy. For [CoFs13-, the A. value is only about 37
kcal/mole, while in [CO(NHs)a13+ AO is about 66
kcal/mole. In agreement with these facts, [CoF6Ia-
has four unpaired electrons, while [CO(NH~)~]'+ has
none. For the d6 configuration in the Fez+ ion, the
pairing energy is about 40 kcal/mole, while the A.
value in [Fe(NH&12+ is only about 35 kcal/mole.
Therefore [Fe(NHa)slz+ unlike [Co(NH3)6J3+should
have the high-spin configuration with four unpaired
electrons, and it does.
Ligond Field Stabilization Energies
The fact that for most of the d" configurations the
electrons do not occupy all five orbitals with equal
probability, but instead tend to occupy three of them
in preference to the other two in an octahedral field
(or two in preference to the other three in a tetrahedral
one) has both energetic and structural consequences.
Some of these are sufficiently straightforward that
they can probably he incorporated into an introductory
treatment. Others, however, such as Jahn-Teller
It is possible that under exceptional circumstances, the d*
configuration might become less stable than, say, a. P - 1 s or
dm-'p configuration, which might have a. Merent number of un-
paired electrons. However, no certain instance of such behsvior
is actually known and it is not necesssry to bring this possibility
up in an introductorp treatment of ligand field theory.
effect^,'^ are probably best omitted. In the following
paragraphs, the sort of coverage which might be given
to a few themnochemical topics is outlined; some
structural ones will be similarly discussed in the fol-
lowing part of this section.
The derivation of ligand field stabilization energies
has usually been given with implicit (or explicit)
reference to the idea that the e, orbitals lie s/5A above
and the t2, orbitals 2/0A below the energy which all
the d orbitals would have if they were surrounded by
the same total electrostatic charge but not split-which
would happen if the charge were uniformly distributed
over a sphere instead of wncentrated into six equal
amounts a t the vertices of the octahdemn. This
raising and lowering of the energy of the sets of orbitals
by amounts inversely proportional to their degeneracies
is a manifestation of the general rule of the "preser-
vation of the center of gravity." It is a rigorous result
in the point charge model, but not in a more general
form of ligand field theory in which the orbital split-
tiigs are ascribed to covalent interactions. It is
therefore important to derive all results pertaining to
ligaud field stabilization energies by an argument
which does not in any way use a "center of gravity
rule," although the argument which does so gives
correct results. For example, in a complex where the
ligands have little or no interaction with the &,orbitals,
the splitting arises mainly or entirely from an upward
shift of the e, orbits (see Fig. 10). A discussion of
ligand field stahilization energies (LFSE's) which uses
only the fact that the energy of the e , orbitals is higher
by A, than that of the &, orbitals in an octahedral
complex may proceed as follows.
For an entire transition series of ions, of given charge,
e.g., Ca2+, (Sc2+), TiZ+, VZ+,. . . Ni2+, CuZ+, Zn2+
(Sc2+is in parentheses because it has not actually been
obtained in an ordinary chemical compound) we
expect a fairly smooth variation of the bond energies
from the dO to the dlQion for the complexes or com-
pounds with a particular ligand or anion. This is
because we expect a fairly smooth variation in the
energy of each type of orbital and hence of the over-
all energy of formation, provided all the orbitals are
either equally occupied in each case or the population
increases uniformly. Now for all the orbitals except
the d orbitals, the populations are constant throughout
such a series. For the d orbitals, the total population
increases steadily, but in the ligand field, there are two
different sets of d orbitals (or d - l i e orbitals) whose
separate populations do not increase uniformly. The
e , population goes from 0 to 4 and if the increase were
uniform, there would be a change of vlo = electron
a t each step. Similarly, a uniform increase in the
population of the t2, orbitals would mean an increase
of 6/10 = 3/6 electron a t each step. On this basis,
the figures for the "uniform" e , and tZ, populations
shown in Table 1 are obtained. Below them are the
actual populations, as indicated in Figure 11, for the
high-spin states. It is clear that for the #, d6, and
dlQcases the "uniform" and the actual populations are
the same, while for all others, the "uniform" populations
give a greater fraction of the total electron density
in less stable e, orbitals and a smaller fraction in the
'O See, for example, COITONAND WILHINBON,
p. 582 ff.
Volume 41, Number 9, September 1964 / 471
 Table 1 . Actual and "Uniform" Orbital Populations in on Octahedral Ligand Field
T o h l "d" electrons 0 1 2 3' 4 5 6 7 8 9 10

Actual populations 0 0 0
i 0 1 2
0
3
1
3
2
3
2
4
2
5
2
6
3
6
4
6
Stability differences 0 / / / ah 0 %/( */I %/I 0

more stable t,, orbitals. Since there are differences in
the occupation of the more and less stable orbitals,
there are differences in the energies of the "uniform"
and the actual configurations.
For the dl case, to go from the uniform to the actual
configuration, 2/6 electron is transferred from the e,
to the tz, orbitals. There is thus a stability increase
(energy decrease) of 2/6An. Again, for the d' case,
electron is transferred from e, to t,, orbitals, caus-
ing an increase of 4/sAo in the stability. The stability
differences so obtained for all the dn ions are listed,
in units of An for each ion, in Table 2.
Table 2. Ligand Field Stabilization Energies in Octahedral
and Tetrahedral Liaand Fields
No. of -LFSE'-
electrons Oct
mental points for the do, dS, and dlo ions, that is, to
the values which would be interpolated for other ions,
if those ions had "uniformly" filled &like orbitals.
This is only a first approximation, however, since there
are other effects, such as the non-uniform variation of
ionic radii, to be discussed shortly, which must be
considered; these effects are not believed to be large
(8).
, .
Similar results are obtained for lattice energies and
for the energies of other processes where complexes
are formed; see George and McClure for general
background and reference (9) for some more recent
results. By reasoning analogous to that embodied
in Table 1, the LFSE's for tetrahedral complexes can
be deduced. These are also given in Table 2.
Tetra

--
a At i s generally < d.for a. given ion with common ligands.

These results may now be compared with some ex-

perimental data. Figure 12 shows the heats of hy-
dration, as given by the reaction:
M"(g) + mH2O (1) = [M(HsO)OI'+(aq)
for all the known dipositive ions of the first transition
series. It is seen that these heats do not vary uni-
formly, though the irregularities are only small frac-
tions ( 1 3 0 kcal/mole) of the total energies (60&
700 kcal/mole). This is because the number of
"non-uniformly" distributed electrons is only a small
fraction of the total number. Further, if a smooth
curve is drawn through the points for the three ions
(Ca2+, do; Mu2+, d5; and Zn2+, dln) which do, in fact,
have uniform populations, all other points lie above
it. Qualitatively, this is just what we should expect.
In all cases, the electrons are equally distributed among
the d orbitals of the free ions, M2+, and in the three
cases, dO, d6, dln they continue to be so distributed in
the [M(HzO)a12+ ions; in the remaining cases, they
move completely or more completely to the more
stable orbitals, thus releasing additional energy.
These additional energies are called ligand field stabili-
z a t i a energies, LFSE's. If the values of An are known
(as they are from spectral data, see later) the LFSE's
can be calculated, and when they are subtracted from
the actual heats of hydration, points are obtained which
lie very close to a smooth curve through the experi-
472 / Journal of Chemical Education
I I I I I I I I I I I
Ca Se T i V Cr Mn Fe Co Ni Cu Zn
Figure 12. Hydrotbn energies of divalent ions of the flmt trransikn series.
Solid circler are experimental volver; open circles are obtained b y sub-
bacting the calculated LFSE'r from the experimental voluer.
Using the octahedral and tetrahedral results to-
gether, another interesting phenomenon may be
explained. If is known that as we go from Mn2+ to
Zn2+, there are great irregularities in the tendency to
form tetrahedral complexes. Generally speaking there
is an increase, but Co2+is abnormally prone to do so,
whereas Ni2+ especially and also Cu2+ seem defi-
nitely to prefer octahedral coordination. From the
figures in Table 2 these facts may be qualitatively
explained. For Co2+ (d") we have the largest tetra-
hedral LFSE together with an average octahedral
LFSE, while with Ni2+we have the largest octahedral
LFSE together with an average tetrahedral LFSE.
For Cu2+the octahedral LFSE also exceeds the tetra-
hedral by a relatively large amount, but here the
existence of considerable distortions in both the
octahedral and tetrahedral complexes requires caution
in pressing the LFSE argument. It has recently been
found (9) that the LFSE's can almost quantitatively
account for the irregular energies of the processes
[MCL12+(g) + 6 H*O (g) = [M(Hdl)s12+(g) + 4 C1- (9)
Some Stereochemical Consequences
There are two striking examples of the effect of d
orbital splittings ou stereochemistry which can r e a
sonahly be covered in a discussion of LFT a t the
introductory level.
The first is the irregular variation in the radii of
the divalent ions of the first transition series, which
again provide the best grist for our mill, since they have
been most thoroughly studied. The radii of these
ions would be expected to show an overall decrease
since the nuclear charge is increased through the
series, while the electrons added to the d shell screen
one another imperfectly. This overall decrease in
radii is observed, hut, as shown in Figure 13, it is not a
smooth one.
cozt sZ+T ~ +~ n ? +~ e " co2+ N ? + C U ~ + z$+
~ ~ + VcrZt
Figure 13. Relative ionic rodii of the divalent ions of theflrrt transition rer-
ier The Cr2+ cmd Cv2+ points are somewhat uncertain becawe of the
d~rtortedoctohedro in which these ions o r e found.
The occurrence of the two "festoons" is a consequence
of the d electron configurations. We recall that the
tRo electrons are nonbonding electrons (at least to a
first approximation) while the e, electrons are anti-
bonding; that is, their presence tends to weaken and
thus lengthen the metal ligaud bonds. We therefore
expect the metal ligaud bond lengths to be little af-
fected by the presence of k o electrons, hut to he fairly
sensitive to the presence of e, electrons, lengthening
in proportion to the number of such electrons.
In Figure 13, a smooth curve has been drawn through
the points for the dO, d5, and dlo ions. This curve may
be considered to indicate the expected radii for ions
having electrons equally distributed among all the d
orbitals, as do the d? (all orbitals empty), d5 (all
orbitals half-filled), and dlo (all orbitals completely
filled) ions. Thus, for Tiz+, the dZion, this would be
the radius if it had v6
electron in the e, orbitals;
actually the d2 ion has no electron a t all in the e ,
orbitals, the bonds to the ligands are therefore shorter
and the radius of the ion is taken to be less than the
value indicated by the curve. For the d3 ion, VZ+,the
actual nuniber of e, electrons is 6/5 less than the number
corresponding to the curve and the actual radius is
again, and even nmre markedly, less than that in-
dicated by the curve. In the next two ions, which
have t,,ae, and tlg3eC2configurations, the number of
e, electrons increases and reaches the value correspond-
ing to the curve. I n the second half of the group,
the same sequence of configurations recurs, super-
posed on the t ~ , ~ configuration
e,~ reached a t MuZ+,and
the second festoon thereby results.
The second striking structural result of d orbital
splitting is found (10) among the class of compounds
called spinels. These are oxides whose most general
formula is ABC04, where A, B and C are cations, the
sum of whose charges is +8. I n many cases, such as
the mineral spinel, MgAh04, which gives its name to
the class, B = C , and in still others, all the cations have
the same atomic number, e.g., FeaOd, MnnOi and CoaOa.
The spinel structure can be described as a cubic close-
packed array of oxide ions with one-third of the cations
~ n ~ c u ptctrah~drsl
v i ~ ~ ~ iittcrsticc.; and the r e ~ l ~ n i utwo
i~~g
thirdsoc~:~~pyingoctnhair~lintersticcs.~~ 'll~c~mmnal"
spinel structure, when the charges on the ions are +2,
+3 and +3, has the +2 ions in the tetrahedral holes and
the +3 ions in the octahedral ones, and it can he shown
that for ions which are spherical this arrangement should
be, to some slight extent a t least, the favored one.
There are cases, however, in which the divalent ions
occupy octahedral holes along with half the trivalent
ions, while the other half of the trivalent ions go into the
tetrahedral holes normally occupied by the divalent
ions. In every case where such an inversion has been
found, it can be explained in terms of LFSE's. For
instance, Fe30ais inverted, while Mn3O4and CosOl are
normal. To invert Mn304, A h a + ions which are in
octahedral holes, would have to be transferred to
tetrahedral ones, with a loss in LFSE (see Table 2),
while A h 2 + ions, which have no LFSE in either en-
vironment, would have to be shifted from tetrahedral
to octahedral holes. Thus, the overall result would
he a loss of LFSE, and inversion does not occur. For
Co301, inversion would be extremely disfavored, due
to the large LFSE's of both the low-spin Co3+ ions
in the octahedral holes and the Co2+ ions in the tetra-
hedral ones, and, again, it does not occur. For Fea04,
however, the inversion is favorable insofar as LFSE
goes, since transfer of high-spin d6Fea+from octahedral
to tetrahedral holes carries no penalty, while transfer
of high-spin d6 Fez+ from tetrahedral to octahedral
holes produces a net gain in LFSE.
Still another example is provided by NiA1104,which
is inverse. Here transfer of AIS+does not change the
net LFSE, hut transfer of Ni2+from the tetrahedral to
the octahedral holes is strongly favored.
It should be emphasized that these inversions could
not have been predicted ab initio, since this would re-
quire more detailed understanding of all the energy
terms than was, or still is, generally available; hut
given the empirical fact that the normal and inverse
structures are similar in stability in the absence of
LFSE effects, we have very good indications of where
and where not to expect inverse structures to occur.
Visible Spectra of rransition Metal Compounds
Surely one of the most striking characteristics of the
transition elements is the fact that nearly all of their
conlpounds are colored and the colors are extremely
varied. Even a t the introductory level-perhaps
especially a t this level-an attempt to explain this, a t
least in correct qualitative fashion, would be worth-
while and interesting to the students. Such an ex-
planation provides a good opportunity to correlate
what may be isolated ideas in the student's minds, for
example, the relationship between the color of a sub-
" A help in visualizing these structures may be the use of
models such as those described by LIMBERT.J. L., J. CHEM.,
Eouc., 41,41 (1964).
Volume 41, Number 9, September 1964 / 473
stance and the positions of its absorption bands, and
the relationships of these in turn to the transitions
between electronic energy levels.
There are however limitations on what can be done,
since a complete understanding of the electronic states
of the multi-electron ions, d2-dS, requires far more dis-
cussion than would seem feasible in the usual introduc-
tory course devoted to a comprehensive survey of
chemistry. I n the following paragraphs, the sort of
coverage which seems to this writer to be feasible is
outlmed.
Wove-Length, Angstrom
4000
0
25.000 20.000
Frequency, c m - '
Figure 14. The visible obrorption spectrum of [ T ~ ( H z O ) ~ ~ ~ + .
The spectra of dl ions can be covered without dfi-
culty. For a d1 ion in a regular octahedral field, the
[Ti(HaO)s]3+ion is a good example; its spectrum,
shown in Figure 14, consists,f only one band centered
a t about 20,000 cm-' (5000 A). This can be identified
as arising from excitation of the electron from the h, to
the e , orbitals, and its energy corresponds to Ao. Thus,
from the spectrum we are able to determine that A. is
20,000 cm-' or 57.2 k ~ a l / m o l e . ~ V hpale,
e red-purple
color of the [Ti(H20)#+ ion is due to the fact that this
absorption band is so placed as to allow most of the
red light and some of the blue light to pass through
unabsorbed and the combination of these two trans-
mission bands produces the red-purple color we see.
Figure 14 also shows where the principal colon occur
in the visible spectrum, which extends, approximately,
from 4000 to 7500 A.
Another good example, which can be demonstrated
easily, of the relationship between color and spectrum
is provided by the NiZ+ion. I n a pale green solution of
nickel sulfate in water, the color is caused by
[Ni(H20)6]z+ ions. On addmg ethylenediamine, the
color turns deep blue, because of the formation of the
[Ni ens]%+ ion. The spectra of these two solutions are
shown in Figure 15. Again a "color map" of the
visible region is given. It is easily seen that
[Ni(HzO)6]2+has a minimum in its absorption where
green light occurs, but absorbs nearly all the res: of the
light seen by the eye; hence it appears green.
[Ni en3I2+, on the other hand absorbs green light
strongly and also yellow, orange, some blue and some
1% For converting spectral energies io their usual units of cm-I
to chemical energies in their usual units of koal/mole, the con-
version factor is: 350 cm-' = 1 koal/mole. Recall that
energy (per mole) = Nhv = Nhc/X.
474 / Journal o f Chemical Education
red light: it transmits onlv blue-~umle
* light and a & -
little red iight.
The spectra of [Ni(H20)612+and [Ni en#+ illustrate
the basis of the spectrochemical series of ligands. Since
the energies of the absorption bands of Ni2+in its com-
ulexes are nro~ortionalto the s~littinzof the d orbitals
by the ligands, it is evident &at theelectrons on the
six nitrogen atoms provided by the three ethylenedi-
amine molecules interact more strongly with the d
orbitals and hence cause a greater energy difference
between the e, and ho orbitals than do the electrons on
the six oxygen atoms of the water molecules. It has
been found that for every transition metal ion of com-
mon occurrence, replacement of 2n H,O1s by n ethylene-
diamines causes the absorption bands to shift to higher
I energies (shorter wavelengths). Moreover, a rather
long list of ligands can be arranged in the order of the
energies of the absorption bands for any given ion and
it is then found that this same order, with, at most,
Wave-Length, Angstroms
2000 4000 6000 8000 ioooo 1200
I I I I I
15,000
50000 25000 15000 10000 8000
Frequency, cm-'
Figure 15. The electronic spectra of [Ni(HnO1sl2+ 1-1 and [Ni en#+
( - - - - - - ) . A "color mop" of the visible region is olro given.
only slight and occasional deviations, is obtained for all
the common transition metal ions. This ordering of
ligands is called the spectrochemical series, and is as
follows, for some of the more familiar ligands:
I- < Br- < C1- < H.0
NH, -
-many other oxygen liganda <
many nitrogen ligands < en < CN-
The existence of such a consistent order of d orbital
splittiugs would not necessarily have been predicted
theoretically, but it is plausible. It is of considerable
value in understanding, correlating and interpreting
many observable changes which occur when ligands
are added to solutions of transition metal ions.
For metal ions with more than one d electron, de-
tailed explanation of the observed absorption bands
seems beyond the scope of an introductory course.
For such ions, there are more than two ways (con-
figurations) of arranging the d electrons in the orbitals
and each of these configurations gives rise to more than
one energy state, because the electrons interact with
one another in various ways, as well as with the nucleus
and with the ligands. Perhaps the nickel(I1) ion can
be used to illustrate, though not explain, the nature of
this rather complex situatio~~.
There are three possible configurations for eight d
electrons in an octahedral ligand field: tzO6eez (most
stable), hq6ee,3 (next most stable), and hO4e,' (least
stable). When all of the possibilities for interaction
between the electrons are considered i t is found that
the hO6eszconfiguration gives rise to one state with two
unpaired electrons, which is most stable, but also to
two other states in which the two e, electrons have their
spins opposed. The tz,5e,a configuration gives rise to
four states, two of which have two unpaired electron
spins. The highest energy configuration, t2,4e,4, gves
rise to four states, only one of which has two unpaired
electron spins. Since there is a general rule in molecu-
lar quantum mechanics that significant absorption of
light can occur only when the resulting transition of
electrons takes place without change in the number of
unpaired electron spins, the appearance of just three
absorption bands in the spectra of octahedrally co-
ordinated Ni2+ ions is easily understood. The transi-
tions are from the state of the tz,Be,2 configuration with
two unpaired electrons to the two states of the hs6e,s
configuration with two unpaired electrons and to the
one state of the tzC4ee,4configuration which has two
unpaired electrons.
Epilogue
With due acknowledgment to G. B. Shaw for the
inspiration, it might be said that theories of chemical
bonding-neglecting not a few which are entirely value-
l e s s f a l l into one of two categories: those which are too
good to be true and those which are too t m e to he good.
"True" in this context is intended t o mean "having
physical validity" and "good" to mean "providing use-
ful results, especially quantitative ones, with a relatively
small amount of computational effort." The proper,
rigorous wave equation for any molecular situation
represents a theory of that situation which is too true
to be good. Most theories which are too good to be
true are those in which the real problem per se is not
treated, but rather an artificial analogue to the real
problem, contrived so as to make the mathematics
tractable, is set up and solved.
The electrostatic crystal field theory, using the point
charge approximation, is such a theory-at its best, or,
Volume 41. Number 9, Sedember 1964 / 475
 A Selected Annotated Bibliography
Essentiolly Nonmofhemoficol Comprehensive Accounts
COTTON, F. A., AND WILKINSON, G.,"Advanced Inorganic Chem-
istry, A Comprehensive Text," Intmcience, New York,
1962. Chapter 26 gives a. general account of LFT suitable
for undergraduate students, though probably not for the
average freshman without supplementary material. Chapter
29 on the elements of the first transition aeries discusses the
electronic structures of many compounds and complexes in
terms of LFT.
ORGEL,L. E., "An Introduction to Transition Metal Chemistry,
Ligand Field Theory," John Wiley, New York, 1960. Covers
virtudly all aspects of LFT in a. lucidly nonmsthematiesl
way. Suitable for most undergraduates, but the average
freshman will need assistance.
DUNN,T. M., in "Modern Coordination Chemistry," J. LEWIS
AND R. G. WILKINS, Editors, Interscience, New York, 1558.
A superb treatment, though more sophisticated than either
of the two preceeding ones.
SUTTON,L. E., J . CHEM.,EDUC..37, 498 (1960). Informative
short rkumi..
PEARSON,R. G., Rec. Chem. Prog. 23, 53 (1962). Informative
short r6snm6.
Mathematical Comprehensive Accounts
BALLHAUSEN, C. J., '.Introduction to Ligand Field Thwry,"
McGraw-Hill, New York, 1962. A mathematical develop-
ment which begins a t a point appropriate for any graduate
chemist with some knowledge of quantum theory in general
and the Slater-Condon theory of atoms in particular (the
summary account of which, in Chapter 2, is more a meapitula-
tion than an introduction). It develops all principal aspects
of the subject assuming only the normal chemist's training and
ability in mathematics. It concludes with an excellent review
of the experimental data an spectra and magnetism. An
excellent book for the serious student.
GRIFFITH,J. S., "The Theory of Transition Metal Ions," Cam.
bridge Univ. Press, Cambridge, England, 1961. An elegant
book, but uery sophisticated. Primarily for those with s
strong background in phyaics and mathematics and a desire
to go very deeply into the theory.
Articles or Monographs on Speciol Topics
Group Theoretical Basis of LFT. COTTON,F. A,, "Chemical
Applications of Group Theory," Interscience, New York,
1963. Chapter 8. Recapitulates in wntemporary notation
and more didactically the basic symmetry considerations first
expounded bv Bethe. Also an introduction to the inter-
pr&ation of polarized spectra:
T h m d y n a m i c Crmwquences qf LFT. GEORGE, P., AND
MCCLTTRE, D. S., Progress in Inorganic Chemistry," 1701. 1,
F. A. COTTON,Editor, Interscience, New York, 1959, p 381.
Thirris still the definitive article on the subject. I t is bothlucid
and thorough.
Pa~amapnefieResonance. Low, W., "Paramagnetic Resonance
in Solids," Academic Press, New York, 1960. Tightly written
and thorough. Develops LFT as it is needed for interprets-
tian of electron suin resonance (ESR) . . data and reviews the
ESR literature in detail.
Kinetics and Mechanism. B a s o ~ o ,F., AND PEARSON,R. G.,
"Mechanisms of Inorganic Reactions," John Wiley, New York,
1958. Gives a thorough discussion of the bearing of LFT on
interpretation of kinetic data for reactions of complexes.
PEARSON, R. G. J. CHEM.EDUC.,38,164 (1961). Gives amore
recent brief outline.
Struclural Consequences of LFT. DUNITZ,J . D., AND ORGEL,L.
E., "Advances in Inorganic and Radiochemistry," Vol. 2, H. J .
EMELOUSand A. G. SHARPE.Editors. Academic Press. New
r , 9 0 1. 1 Good suwrnary and e x p l ~ u ~ t i ~ m the uae
01 I.FT 11, interpret wlut are prcsu~s.ublyJilln-Teller efler.ts i u
the struc tun.* of trmsit~onmet31 compounds, ns well n s other
structural phenomena.
Molecula7 Orbital T h e w . GRAY,H. B., J. CHEM.EDUC.,41,
2 (1964). An explanation of the MO treatment of complexes
in its simple LCAO fonn and a snrvev of results.
~aramagne& Resonance. CARRINGTON, A,, AND LONGUET-
HIGGINS,H. C., Qumt. Rev., 14, 427 (1960). A lucid, quali-
tative introduction.
.11ngnd,~rn I.I:WIS,.I., .ASD FIGGIS, n. S . ,"I'rope~s ih I u w ~ m i v
U1eni19rr?.,"Vd. 6 , F. .\. (.'OTMN,Editor, Interarience, Sen.
l ork, 1964. 'l'1.e best nrrd most tirrwly expodion of theory
and fact for the inorganic and physical chemist.
NephelauzeticEffects. JYIRGENBON, C. K., "Progress in Inorganic
Chemistry," Vol. 4, F. A. COTTON,Editor, Interscience, New
York, 1962, p. 73. A mine of useful data. analyzed in depth.
Covers everything from the general idea to the controversial
fine points.
Optical Rotatory Dispersion. WOLDBYE, F., Ree. Chem. Pmgr.,
24, 197 (1963). An excellent introduction to theory and facts.
Volume 41. Number 9, Sedember 1964 / 475
perhaps, a t its worst. It is a gift horse which, when to present, consciously, a facile untruth, however much
looked straight in the mouth, is found to have false it may help in "putting the subject across." I hope
teeth. There is no physical validity to it even though that readers who agree with this premise will find this
it is mathematically convenient and L'works" UP to a discussion useful in avoiding some of the untruths
point. about ligand field theory.
Thus, the conceptually simple picture which has
traditionally been employed in introducing the idea of Literature Cited
d orbital splitting can no longer be used unless one is
(1) BECQUEREL, J., Z. Phy~ik.,58,205 (1929).
willing to perpetrate a deliberate and conscious de- 12) BETHE.H.. Ann. Phvsik 151. 3. 135 11929)
ception. Naturally, it has long been recognized that BAL~AUS;N,C. J.; K&." ~ a n s k b ~ l d m s k a b . Selskab,
the crystal field theory could not be taken literally; Mat. Fys. Medd., 29, No. 4 (1954).
that is, that a purely electrostatic treatment of com- The qualitative argument given here is based on the calcu-
lations of KLEINER,W. H., J. C h m . Phys., 20, 1784
plexes and crystals which took no account a t all of (1952) and FREEMAN, A. J., A N D WATSON, R. E., P h y ~ .
covalent character in the metal-ligand bonds was not Rev., 120, 1254 (1960).
entirely correct. But it was generally assumed that J~GENSEN C., K., PAPPALARDO, R., AND SCHMIDTKE,
the electrostatic approach was partially or qualitatively, H.-H.. J. Chem. Phvs.. 39.1422 11963).
perhaps, in some cases, even semiquantitatively valid,
and thus perfectly legitimate for use a t least as a first
SUGANO, 'S., &ULM~;
~ N D R. G:, phis. Rev., 130, 517
110fi3iRi.
\ - - ~ - , ~

approximation, or as a half truth which further study (8) HUSH,N. S., AND PRYW,N. H. L., J. Chem. Phys., 28,
would not contradict, but merely qualify and enlarge 244 (1958).
upon. I believe that most teachers a t some time find it (9) BLAKE,A. B., AND COTTON,F. A., Inorg. Chem., 3, 5
(1964).
necessary to use the general approach of beginning a
(10) MCCLURE,D. S., P h y ~Chem. Solida, 3, 311 (1957); Du-
topic with a facile half truth and that this is fair prac- NITZ, J. D., AND ORGEL,L. E.,Phys. Chem. Solids, 3,
tice. I do not believe, however, that it is ever justified 318 (1957).

Qualitative Organic (?) Chemistry

In a certain chemistry building there are five labs, all in a. row, each painted a different color
and each containing a special item of apparatus. A different chemist works in each lab and keeps
the main stock of one solvent and one reagent. The following information is sufficientto tell who
has the acetone and where the gas chromatograph is located. (Struggle a bit. We'll tell you
next month.)
Fisher works in the red lab.
Grignard has the infrared spectrophotometer.
Ethyl ether is in the green lab.
Kekule has the benzene.
The green lab is immediately to the right (your left) of the ivory lab.
The chemist with the phenylhydrazine has the magnetic stirrer.
The iron (111) chloride solution is in the yellow lab.
The alcohol is in the middle lab.
Friedel works in the first lab on the left.
The chemist who has the phenyl isocyanate works in the lab with the sublimation furnace.
Iron(II1) chloride solution is kept in the lab next to the lab with the sublimntion furnace.
Tollens reagent is in the same lab as the chloroform.
Lucss keeps the supply of Lueas reagent.
Friedel works next to the blue lab.
Submitted by PROF.JAMESG. TRAYNHAM
Loursr~ STATE
~ ~ UNIVERSITY

476 / Journal o f Chemicol Education