Resource Papers-I

Prepared under the sponsorship of

The Advisory Council on College Chemistry

F. Albert Cotton
Massachusetts Institute of Technology
Field Theory
Cambridge, Mass.

The presentation of ligand field theory in causes, but for most undergraduate courses—and cer-
the first college chemistry course cannot be said to be tainly for the introductory course—such rigor and com-
essential. If time is limited, or if the ability of the prehensiveness are unnecessary.
students and/or their interest in chemistry as a pure
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science rather than as a branch of useful knowledge are Causes of Inner Orbital Spittings
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not well above average, I believe there are many other The possibility that the degeneracy of atomic orbitals
topics which can be more profitably discussed. There will be significantly split when an ion is placed in a
is time enough in later years of the chemistry cur- chemical environment was first suggested by Bec-
riculum for those who do elect chemistry as a major querel (1) and the problem was then examined in con-
subject to tackle this aspect of it. However, in a siderable detail by Bethe {2). Bethe’s work consists
thorough sort of course, taught to a select, science- of two parts: first, in one of the earliest applications of
oriented group of students, the subject of ligand field symmetry arguments to a chemical problem, Bethe
theory might form an interesting and stimulating part. determined the qualitative nature of the orbital split-
Certainly it is an important part of the “vocabulary” tings for various important geometries. These quali-
of modern theory which teachers should know so that tative results are correct whatever the mechanism
their presentation not be erroneously simplified at any (electrostatic, or covalent, as discussed presently)
level. It is important, however, to present it in such which brings them about. For d orbitals, in several
a way as to avoid creating false impressions about
important geometrical situations, they are as follows:
the nature of ligand-to-metal bonds; this requires of the
In both octahedral and tetrahedral surroundings, the dZVl
teacher, first, an awareness and understanding of the dzz, and dvz orbitals remain equivalent, as do dx*-yz and dzs
dangers and, second, the possession of some concrete orbitals.
ideas about how to avoid them. This article presents In square surroundings, the dzi and dvz orbitals remain equiva-
an outline of ligand field theory in its present state and lent, but the dzy, dxi~yz and dzt orbitals are not equivalent to any
at an introductory level; it suggests, partly in precept others.
and partly in example, a presentation of this subject Bethe obtained these and other results by formal,
which is primarily intended to be appropriate in the group-theoretical methods, but they can also be ob-
general chemistry course, but it also raises some points tained, or at least their correctness strongly suggested,
which will be of concern to those introducing ligand
field theory to students at any level.
“Resource Papers” is a series being prepared under the
Ligand field theory can be defined as the theory of (1) sponsorship of the Advisory Council on College Chemistry
the origins and (2) the consequences of the splitting of as one of the activities of the Teaching Aids Panel. The
inner orbitals of ions by their surroundings in chemical Advisory Council on College Chemistry (AC3) is supported
compounds. In this article we shall restrict attention by the National Science Foundation. Professor Charles C.
primarily to penultimate d orbitals, i.e., the 3d orbitals Price, of the University of Pennsylvania, Philadelphia,
Penna. 19104, is the chairman.
for ions of the first transition series, 4d and 5d orbitals
for ions of the second and third transition series. To a Single copy reprints of this paper are being sent to
considerable degree, it is possible to deal with the two chemistry department chairmen of every U.S. institution
offering college chemistry courses and to others on the mail-
parts of ligand field theory separately; this has the im- ing list for the ACS Newsletter. Additional single copies
portant consequence that many of the significant and will be sent free to all interested individuals who make
relatively straightforward results of d-orbital splittings, request to the Editor of the ACS Newsletter:
e.g., ligand field stabilization energies, stereochemical Professor E, L. Haenisch
preferences and, of course, spectroscopic and magnetic Department of Chemistry
Wabash College
behavior, can be discussed pragmatically without neces- Crawfordsville, Indiana 47933
sarily going very far into the inherently difficult and Multiple copy orders (in lots of. 10) can be filled if
tedious question of what causes the splittings. Of accompanied by remittance of $1,50 per unit of 10 copies.
course, a truly rigorous discussion of all the conse- Orders must be addressed to Professor Haenisch, not to the
quences of inner orbital splittings could not be given Journal of Chemical Education.
without intimately interweaving an examination of the

466 / Journal of Chemical Education

by informal, pictorial arguments, requiring only the Similarly, for a tetrahedral set of four ligands, ar-
common sense* any bright freshman should have.
1
To ranged shown in Figure 4 at alternate vertices of a
as
do so, it is first necessary to present pictures showing cube,3 it can be seen that the dxy, dxz, and dyz 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 de« orbital with their lobes pointing to cube edges, while the
can be regarded as a combination, in equal parts, of two
orbitals, dst-xi and dz*~y*, each of which is shaped like
the other four d orbitals; this is illustrated in Figure 2.2
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 six ligand atoms in an octahedral com-

plex in relation to the same Cartesian coordinate system used in Figures 1

nd 2 for the d orbitals.

Figuie 1. Balloon pictures of the conventional set of d orbitals. The sur-

faces are drawn to enclose a major pari—say, roughly, 90%—of the
amplitude of the wave functions. The sign of the wave functions in each
lobe is shown. Since the distribution of electron density is given by \p2, it
will in each case be quite similar to the shape of the wave functions of the
orbitals.

Figure 4. The arrangement of the four ligand atoms in a tetrhaedral com-

plex in relation to the same Cartesian coordinate system used in Figures 1
and 2. Note how the tetrahedron is composed of four alternate corners of
a cube.

Figure 2. Drawings showing how the dz2 orbital consists of a d32—z2 and
a dj2_v2 orbital in equal proportions.

It should not be hard to see that the dX2-y%, dzi-xi, and

dz* V2 orbitals are all oriented in one way in relation
-

to the six ligands, while the dxy, dxz, and dyz 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 dxy, dxz, and dyz orbitals are
equivalent to one another, whereas the dxi~yt and dzt Figure 5. The arrangement of four ligand atoms in a square complex in
(being made up of equal parts of the equivalent pair relation to the same Cartesian coordinate system used in Figures 1 and 2.
dzt-xdzi-„z) are different from the first three, but
equivalent to one another. dxz-yi, dzz^xZ, and dzi-yi orbitals stand in another re-
1
Someone ia supposed to have remarked that “group theory
lationship; namely, their lobes point to the centers
of cube faces. Hence, again, we conclude that dxv,
is just organized common sense,” which is not too great an
exaggeration. dxz, dyz form one equivalent set while dxZ^y2 and dz* form
1
For algebraic details, Bee Cotton and Wilkinson, page a second equivalent set.
973i It is necessary to make this breakdown of the dz* orbital Finally, it can be seen that the dxz and dyz orbitals
in order to demonstrate by the pictorial argument that dz* and both have the same relationship to the ligands set at the
dx* y* are not only different from the other three, but also are
of a square in Figure 5, that both dzt-xt and
—

corners
equivalent to one another. It is to be stressed, however, that the
dzi—x* and dz2-y* orbitals have no actual existence along 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 besides the present one, is worth emphasizing.

Volume 41, Number 9, September 1964 / 467

d^-y2 have a second relationship to the ligands and Bethe’s point charge model, actually spend a part of
that each of the two remaining orbitals is related in their existence in orbitals “belonging” to the ligand
still different ways. atoms.5 Such results imply that there is covalence in
The question now arises as to how much the energies the metal-ligand bonding; some of the data permit
of the nonequivalent orbitals, or sets of orbitals, may quantitative estimation of the amount of covalence.
differ. It must be assumed that if two orbitals, even From the theoretical side, the inadequacy of the
if intrinsically similar, are differently oriented toward point charge model (as other than a physically mean-
their surroundings, there will, in principle, be some ingless formalism leading to useful equations) may be
difference in the energy of an electron depending on described as follows %), First, let us recognize that the
which of them it occupies. ligand atom is not a point. It is an object of about the
The second part of Bethe’s paper offered an answer to same size as the metal ion and it is built in the same
this question based on the assumption that the ligands way. An F_ ion, for example, consists of a positive
can be treated as point negative charges, a model which nucleus of charge +9e, which is essentially a point,
has often been considered to represent the chemist’s surrounded by a spherical cloud of total charge lOe, —

concept of purely ionic bonding. (In fact, it does not, about 90% of which lies within a sphere whose radius
as will be seen.) Using this model, it is easy to see that is about equal to half the M—F distance in an MF„
qualitatively, an electron in an orbital whose lobes complex ion or in a MF„ salt.
point at the negatively charged ligands will have a
higher electrostatic potential energy than an electron d .2 _,2
in an orbital whose lobes point between ligands. In d,2-y2 d,2
b|5
other words, the former orbital is a less stable one and eg( dxy, dxz dyz
lies higher on an energy level diagram of the usual type '2 { —:}
than does the latter orbital. Figure 6 illustrates these T
results for the octahedral, tetrahedral and planar cases. A.o At
“29
It should be noted that for the square environment, the dx2-y2 dz2
ordering of the orbitals is not exactly fixed by the sym- {- =1 1
metry alone, but depends in certain respects (e.g., as to dxy, dxz dy dz2
whether the d# orbital lies above or below the dxy °I9
I ’28 {------~}
orbital) on the physical details. The arrangement dxz dv
shown in Figure 6 is the one believed to be correct in {- —
1

most real cases. Move generally, the relative stabilities

Octahedral Tetrahedral S quare
of a series of inherently similar orbitals will vary in-
Figure 6. Orbital splitting diagrams for the three most important types of
versely according to the extent to which they bring complex. Orbitals within each pair of braces are of identical stability.
the electron into proximity with the negative ligands.
The argument may be generalized to include not only The point charge model does not meaningfully
negatively charged ligands, but dipolar ones, which will correspond to the concept of ionic bonding because a
be so oriented as to have their negative ends closer
point charge does not meaningfully represent the
than their positive ends to the metal ion. Bethe way one ion “looks” to the outer electrons on another
showed further that the actual magnitudes of the ion which is within about two A of it.6 However, a
energy differences (e.g., A0 and A, in Figure 6) can be reasonable representation of a purely electrostatic
calculated using this electrostatic model if one can interaction between the d electrons of a cation and an
select the proper magnitudes for the metal-ligand dis-
anion, is that given in Figure 7, where the anion is shown
tance, and the ligand charge (or dipole moment) and as an entity with structure and finite size, as described
assign an appropriate radial part4 to the wave function above. Using this qualitatively realistic representa-
for the d orbitals. In relatively recent times, Ball- tion of the physical situation, the following argument
hausen (3) showed that if these parameters arc assumed
may be developed.
to have the same values in an octahedral complex,
MXe and a corresponding tetrahedral one, MXf, The evidence will not be reviewed here. Several summaries
s

the ratio of A; to A0 will be 4/9. It has also been shown are cited in the bibliography. Those in Orgel, Ballhausen,
that the absolute values of A0 (or A,) can be obtained and Cotton and Wilkinson are especially recommended.
within a factor of less than two by choosing reasonable
6
To more deeply buried electrons of a cation, a near neighbor
anion may come closer to appearing as a point negative charge.
values for the various parameters required. Recall in this connection a basic theorem of electrostatics, due to
However, in spite of all this sort of pragmatic success, Gauss, which states that if a test charge lies completely outside
this electrostatic model is now known to be unrealistic of any charged sphere, it experiences the same force as it would
and ultimately unsatisfactory. It has been discredited if all the charge on or in the sphere were concentrated in a point
at the center of the sphere. For the rare earth ions, calcula-
both experimentally and theoretically. The experi- tions of orbital splittings using the point charge model may there-
mental evidence against it comes from a variety of fore have somewhat more physical meaning, although there is
sources all showing that electrons which are supposed evidence (5) to show that here, too, covalence plays a role. The
to be entirely in the metal ion d orbitals, according to 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 computation of the electrostatic effect produced
*
When an orbital wave function is expressed in spherical by an array of ions in a crystal which lie outside of the first co-
coordinates ip(r, 0, <t>)
=
R(r)Q{$)®{<t>), the radial part is the R{r). ordination shell of the cation being treated. Even for second
The parameter r measures the radial distance from the origin. nearest neighbors, however, some significant covalence effect,
The angular part of the wave function is &copy;(0)<f>(0) which involves or orbital overlap, evidently occurs as shown by the existence of
the direction in space from the origin and depends only upon the a contact shift (6) in the nuclear resonance frequency of l70 in
angles 0 and <£. the ion pair or “outer sphere complex.”

468 / Journal of Chemical Education

 Aii electron occupying an orbital which has lobes dominantly the characteristics of the lower energy
such as A and A' in Figure 7, directed at the ligand atomic orbital, while the resulting antibonding orbital
atoms will feel the positive charge of the nucleus (or the will have predominantly the characteristics of the higher
net positive charge of the compact core, in a heavier energy atomic orbital: this is represented in Figure
atom) rather strongly, thus off-setting appreciably 8b. However, if the two atomic orbitals (^, <j in
the repulsive effect it feels from the diffuse electron Fig. 9) are of such a nature that they have no net
cloud into which it penetrates. On the other hand, 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„ orbitals7 of a metal ion and the <r orbitals of
ligand atoms, while the relationship shown in Figure 9
is that between the t->a orbitals of a metal ion and the
<r orbitals of ligand atoms. The complete result, a
combination and elaboration of Figures 86 and 96
is shown in Figure 10.

Figure 7. A drawing of part of a complex showing two lobes. A, A' of an

eg type metal orbital, two lobes, B, B' of a fzB type metal orbital and two
ligand atoms. The spheres enclosing most of the electron clouds of the lig-
and clouds of the ligand atoms are also shown.
Figure 8. Sketch showing the formation of bonding and antibonding ir
type orbitals, such as those formed by overlap of metal eg orbitals with
an electron occupying an orbital which has lobes, such appropriate ligand orbitals in octahedral complexes.
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
(a) (b)
slightly in favor of orbital A. Actual calculations, using
Figure 9. Sketch showing the lack of interaction between a a orbital (such
realistic (i.e., Hartree-Fock) orbitals for metal and as a tig orbital of a metal ion) and a ligand <r orbital.

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 d Orbitals
represents “ionic bonding”) we cannot explain the (l2q.eg)
observed splittings of d orbitals.
It has been shown, however, that when the effects a- Orbitals

of covalent bonding are introduced, they give a splitting

which is qualitatively correct and, if sufficiently elabo- Figure 1 0. Energy level diagram showing the results of all the interactions
between the a orbitals of a ligand and the t20 and eg orbitals of a metal
rate calculations are made (very elaborate, unfor-
tunately), almost quantitatively correct results can
be obtained (7). Now it can be seen that by considering the overlap
It is not very difficult to see, at least qualitatively, of orbitals, we have arrived at the same qualitative
that covalent bonding will operate in this way. When result as that given by the point charge electrostatic
each of two atoms has an orbital directed toward the
model: the fivefold degeneracy of the d orbitals is
other one (<ri, <n, Fig. 8a), and these atoms approach
to within a few Angstroms of one another, the orbitals
split in an octahedral environment, so that the e„
orbitals become less stable than the UB orbitals. For
become mixed to form two new orbitals, one, (o-B), all of the principal chemical consequences of orbital
having relatively high amplitude (high electron con- splittings, if is only necessary to know the correct
centration) between the two nuclei and the other, (o-A), ordering of the orbitals; the actual magnitude of the
having relatively low amplitude (low electron concentra-
tion) between the nuclei. When electrons occupy 7
The symbolism here adopted is that now most generally
the first, (a bonding orbital), the atoms become bound accepted. Readers need not worry about its full implications
together, while when electrons occupy the second, which derive from the use of Mullikan symbols and character
tables to describe molecular symmetry. The e implies a two-
(an antibonding orbital) a repulsive or antibonding
dimensional representation, t, a three-dimensional representa-
force is set up. Furthermore, if the two atomic
tion: g (from the German gerade, meaning even) implies even
orbitals with which we begin have rather different symmetry with respect to inversion. (See Cotton, F. A.,
energies, the resulting bonding orbital will have pre- “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 tig orbitals, is
determined in some one experiment and the results of 2 A or the low-spin configuration fe,6 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 d7 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 arising from Pauli’s exclusion principle and from
interelectronic repulsions. The former require no High-spin Low spin -
High-spin Low-spin
special discussion; they are the same as for free atoms States States States States
and ions, For present purposes, the phenomenon of —4-
interelectronic repulsion—which results from both —- -*- -4-
simple coulombic repulsion and from exchange energy —-
—4-
—*-
-4-
variations—can be expressed as follows: the placing t5„e„ ez
of a second electron in an orbital already occupied 29 9 *2g 29 9 29

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, -4-
=i=Jz Z*=**Z
which, to a reasonable approximation, may be con- -4-*“ -4-*—
4 *2 6
sidered a constant for all of the nd orbitals of a given 2g g 2g '2geg *2geg
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 an ion in an octahedral
ligand field for any case from d1 to d9. Similar ar-
guments can be devised for cases where the ligands are
differently arranged, e.g., tetrahedrally, or in a square.
For a d1 ion, the single electron naturally goes into
one of the U, orbitals, and the ion can be said to have a Figure 1. Diagrams showing the most stable arrangements of electrons in
1

the d orbitals of ions in octahedral complexes.

configuration. Similarly, d2 and d3 ions will have
tig2 and Ug3 configurations, with each electron in a For a d8 ion, it is impossible to have fewer than three
different tig orbital and all electron spins parallel electron pairs, and the configuration having the greatest
(Hund’s rule8), as shown in Figure 11a. For a d* ion, number of tig electrons, to^eg2, must be the most stable.
there are two possibilities. All electrons may occupy
the ti, orbitals (tig*) but then one orbital must be Similarly, for a d9 ion, the most stable arrangement
must be hg’eg3. By exactly similar arguments, the
doubly occupied and the stability of the configuration results for tetrahedral complexes can be obtained.
is lessened by the pairing energy, P. Alternatively,
we may have the configuration tig3e0 which does not
(Note, by reference to Figure 6, that in this case, the
ea orbitals are lower in energy than the tog orbitals.)
require expenditure of pairing energy, but does re- However, so far as is known at present—and 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 wc have ;2ff3es and if A > P we have f2ff4. The
various dn ions in tetrahedral complexes are the fol-
kg3eg configuration has four unpaired electron spins,
lowing high-spin configurations:
while kg* has only two unpaired electron spins. Accord-
ingly, the former is called the high-spin configuration d':el d':eV dhe%'
and the latter the low-spin configuration. d2:e2 dbeV
For a d5 ion we may have the high-spin tiS3es2 con- dz: eHo1 de:e3t s3 d*:eH is
figuration, in which the total energy expended to put The purely theoretical possibility of a low-spin con-
8
Hund’8 rule, originally established from spectroscopic studies, figuration does exist, however, for the d3-d6 cases.
states that the lowest of several possible 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 =
Zsi, the spin vectors splitting or any specification of the energies of the U.
of the electrons occupying the equivalent orbitals. In effect, and e orbitals relative to any reference energy what-
it means that electrons spread out over a set of equivalent orbitals
with their spins parallel to the maximum possible extent. See, for ever. With these configurations as a basis, it is
example, Herzberg, 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 / Journo/ of Chemical Education

Magnetic Properties effects,10 are probably best omitted. In the following
In order to predict explain magnetic properties
or paragraphs, the sort of coverage which might be given
of a transition metal ion in its complexes or other to a few thermochemical topics is outlined; some
compounds, our first need is always to know how many structural ones will be similarly discussed in the fol-
unpaired electron spins it has or may have. The dis- lowing part of this section.
cussion may then proceed to higher levels of sophistica- The derivation of ligand field stabilization energies
tion if desired, but this basic question of how many has usually been given with implicit (or explicit)
unpaired electrons there are must always be answered reference to the idea that the ca orbitals lie S/5A above
first. and the U, orbitals 2/sA below the energy which all
By referring to the electron configuration diagrams the d orbitals would have if they were surrounded by
in Figure 11, we see first of all that for d1, d2, d3, d8, the same total electrostatic charge but not split—which
and d9 ions in octahedral environments, there will would happen if the charge were uniformly distributed
over a sphere instead of concentrated into six equal
always be 1, 2, 3, 2, or 1 unpaired electrons, respectively,
no matter how great the value of Ao may become.9 amounts at the vertices of the octahderon. This
Deviations from these numbers in the d2, d3 or ds raising and lowering of the energy of the sets of orbitals
cases (provided it is certain they are not due to any by amounts inversely proportional to their degeneracies
intermolecular effects) can be taken to indicate that is a manifestation of the general rule of the “preser-
the environment of the ion actually departs appreciably vation of the center of gravity.” It is a rigorous result
from the octahedral arrangement. in the point charge model, but not in a more general
For d4, d5, d6, and d7 ions, the number of unpaired form of ligand field theory in which the orbital split-
electrons can be either the high-spin ones, 4,5,4,3 re- tings are ascribed to covalent interactions. It is
spectively, or the low-spin ones, 2, 1, 0, 1 respectively, therefore important to derive all results pertaining to
depending on the magnitude of A0 relative to P for ligand field stabilization energies by an argument
the ion in question. Now the value of P for a given which does not in any way use a “center of gravity
ion can be evaluated fairly reliably from data on the rule,” although the argument which does so gives
spectrum of the gaseous ion; P values are, with few correct results. For example, in a complex where the
exceptions, known quantities. Therefore, for a series ligands have little or no interaction with the orbitals,
of complexes of a given ion, some high-spin and some the splitting arises mainly or entirely from an upward
low-spin, we can draw the conclusion that all ligands shift of the orbits (see Fig. 10). A discussion of
giving the low-spin configuration produce A values in ligand field stabilization energies (LFSE’s) which uses
excess of P, while all ligands giving the high-spin con- only the fact that the energy of the e„ orbitals is higher
figuration, produce A values less than P. From the by A0 than that of the t2s orbitals in an octahedral
spectrum of an ion in a given complex, the actual value complex may proceed as follows.
of A can be determined (see below). It has been For an entire transition series of ions, of given charge,
found, without exception, that predictions of the kind e.g., Ca2+, (Sc2+), Ti2+, V2+, Ni2+, Cu2+, Zn2+
. . .

just described are correct. For instance, for the d6 (Sc2+ is in parentheses because it has not actually been
configuration of Co3+, data from spectra of the gaseous obtained in an ordinary chemical compound) we
ion lead to a value of about 50 kcal/mole for the pairing expect a fairly smooth variation of the bond energies
energy. For [CoF6]3~, the A0 value is only about 37 from the d° to the d10 ion for the complexes or com-
kcal/mole, while in [CO(NH3)6]3 + A0 is about 66 pounds with a particular ligand or anion. This is
kcal/mole. In agreement with these facts, [CoFe j3~ because we expect a fairly smooth variation in the
has four unpaired electrons, while [Co(NH3)6]3+ has energy of each type of orbital and hence of the over-
none. For the d6 configuration in the Fe2+ ion, the all energy of formation, provided all the orbitals are
pairing energy is about 40 kcal/mole, while the A0 either equally occupied in each case or the population
value in [Fe(NH3)«]2+ is only about 35 kcal/mole. increases uniformly. Now for all the orbitals except
Therefore [Fe(NH3)e]2+ unlike [Co(NH/jGl3+ should the d orbitals, the populations are constant throughout
have the high-spin configuration with four unpaired such a series. For the d orbitals, the total population
electrons, and it does. increases steadily, but in the ligand field, there are two
different sets of d orbitals (or d-like orbitals) whose
Ligand Field Stabilization Energies separate populations do not increase uniformly. The
The fact that for most of the dn configurations the ea population goes from 0 to 4 and if the increase were
electrons do not occupy all five orbitals with equal uniform, there would be a change of 4/™ 2/s electron
=

probability, but instead tend to occupy three of them at each step. Similarly, a uniform increase in the
in preference to the other two in an octahedral field population of the U_, orbitals would mean an increase
(or two in preference to the other three in a tetrahedral of 6/io 3
=
j electron at each step. On this basis,
&

one) has both energetic and structural consequences. the figures for the “uniform” e„ and populations
Some of these are sufficiently straightforward that shown in Table 1 are obtained. Below them are the
they can probably be incorporated into an introductory actual populations, as indicated in Figure 11, for the
treatment. Others, however, such as Jahn-Teller high-spin states. It is clear that for the d°, d3, and
d10 cases the “uniform” and the actual populations are
9
It is possible that under exceptional circumstances, the d” the same, while for all others, the “uniform” populations
configuration might become less stable than, say, a d"-1® or give a greater fraction of the total electron density
dn_1p configuration, which might have a different number of un- in less stable ec orbitals and a smaller fraction in the
paired electrons. However, no certain instance of such behavior
is actually known and it is not necessary to bring this possibility
up in an introductory treatment of ligand field theory.
10
See, for example, Cotton and Wilkinson, p. 582 ff.

Volume 41, Number 9, September 1964 / 471

 Table 1. Actual and "Uniform” Orbital Populations in an Octahedral ligand Field
Total “d” electrons 0 1 2 3 4 5 6 7 8 9 10

“Uniform” populations 4A 6A 8/s 2 12A 'Vs I8/s 18/s 4

8/s 9/s 12A 3 18/s 21/s 24A "/. 6
Actual populations («„ 0 0 0 0 1 2 2 2 2 3 4
( «!„ 0 1 2 3 3 3 4 5 6 6 6

Stability differences 0 v. Vs 6/s 7s o Ys Vs Vs Vs 0

more stable Ap orbitals. Since there are differences in mental points for the d°, d&, and dL0 ions, that is, to
the occupation of the more and less stable orbitals, the values which would be interpolated for other ions,
there are differences in the energies of the “uniform” if those ions had “uniformly” filled d-like orbitals.
and the actual configurations. This is only a first approximation, however, since there
For the d1 case, to go from the uniform to the actual are other effects, such as the non-uniform variation of
configuration, 2/s electron is transferred from the e„ ionic radii, to be discussed shortly, which must be
to the hg orbitals. There is thus a stability increase considered; these effects are not believed to be large
(energy decrease) of 2/5Ao. Again, for the d1 case, (8).
4/s electron is transferred from e„ to i2j orbitals, caus- Similar results are obtained for lattice energies and
ing an increase of 4/5A0 in the stability. The stability for the energies of other processes where complexes
differences so obtained for all the dn ions are listed, are formed; see George and McClure for general
in units of A0 for each ion, in Table 2. background and reference (9) for some more recent
results. By reasoning analogous to that embodied
Table 2. Ligand Field Stabilization Energies in Octahedral in Table 1, the LFSE’s for tetrahedral complexes can
and Tetrahedral Ligand Fields be deduced. These are also given in Table 2.
No. of --LFSE--.
electrons Oct Tetra
0 0 0
1 2A A0 8A A,
2 Vs Ao Vs A*
3 6A Ao 4A Af
4 Vs Ao Ys A,
5 0 0
6 Vs Ao Vs Aj
7 Vs Ao ‘A
4
A,
8 Vs Ao A Ai
9 Vs Ao 7s A,
10 0 0
-
A, is generally ^ l/* Ao 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:
Figure 2. Hydration energies of divalent ions of the first transition series.
M*+(?) + osH20 (i)
1
[M(H20)o]2+ (a?)
=
Solid circles are experimental values; open circles are obtained by sub-
for all the known dipositive ions of the first transition tracting the calculated LFSE’s from the experimental values.
scries. It is seen that these heats do not vary uni-
formly, though the irregularities are only small frac- Using the octahedral and tetrahedral results to-
tions (<30 kcal/mole) of the total energies (600 gether, another interesting phenomenon may be
700 kcal/mole). This is because the number of explained. If is known that as we go from Mn2+ to
“non-uniformly” distributed electrons is only a small Zn2+, there are great irregularities in the tendency to
fraction of the total number. Further, if a smooth form tetrahedral complexes. Generally speaking there
curve is drawn through the points for the three ions is an increase, but Co2+ is abnormally prone to do so,
whereas Ni2+ especially and also Cu2+ seem defi-
(Ca2+, d°; Mn2+, d5; and Zn2+, dln) which do, in fact,
have uniform populations, all other points lie above nitely to prefer octahedral coordination. From the
it. Qualitatively, this is just what we should expect. figures in Table 2 these facts may be qualitatively
In all cases, the electrons are equally distributed among explained. For Co2+ (dr) we have the largest tetra-
the d orbitals of the free ions, M2+, and in the three hedral LFSE together with an average octahedral
cases, d°, dfi, d10 they continue to be so distributed in LFSE, while with Ni2+ we have the largest octahedral
the [M(H20)6]2+ ions; in the remaining cases, they LFSE together with an average tetrahedral LFSE.
For Cu2+ the octahedral LFSE also exceeds the tetra-
move completely or more completely to the more
stable orbitals, thus releasing additional energy. hedral by a relatively large amount, but here the
These additional energies are called ligand field stabili- existence of considerable distortions in both the
zation energies, LFSE's. If the values of Ao are kuown octahedral and tetrahedral complexes requires caution
in pressing the LFSE argument. It has recently been
(as they are from spectral data, see later) the LFSE’s
can be calculated, and when they are subtracted from found (9) that the LFSE’s can almost quantitatively
the actual heats of hydration, points are obtained which account for the irregular energies of the processes
lie very close to a smooth curve through the experi- [MCh]2+ (?) + 6 H20 (?) =
[M(H20)6]2+ (?) + 4 Cl- (?)

472 / Journal of Chemical Education

Some Stereochemical Consequences called spinels. These are oxides whose most general
There two striking examples of the effect of d
are
formula is ABC04, where A, B and C are cations, the
sum of whose charges is +8. In many cases, such as
orbital splittings on stereochemistry which can rea-
the mineral spinel, MgAl204, which gives its name to
sonably be covered in a discussion of LFT at the
the class, B =
C, and in still others, all the cations have
introductory level. the same atomic number, e.g., Fe304, Mn304 and Co304.
The first is the irregular variation in the radii of
the divalent ions of the first transition series, which The spinel structure can be described as a cubic close-
again provide the best grist for our mill, since they have packed array of oxide ions with one-third of the cations
been most thoroughly studied. The radii of these occupying tetrahedral interstices and the remaining two
ions would be expected to show an overall decrease thirds occupying octahedral interstices.11 The “normal”
since the nuclear charge is increased through the spinel structure, when the charges on the ions are +2,
series, while tire electrons added to the d shell screen
+3 and +3, has the +2 ions in the tetrahedral holes and
one another imperfectly. This overall decrease in the +3 ions in the octahedral ones, and it can be shown
radii is observed, but, as shown in Figure 13, it is not a that for ions which are spherical this arrangement should
smooth one. be, to some slight extent at 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, Fe304 is inverted, while Mn304 and Co304 are
normal. To invert Mn304, Mn3+ ions which are in
octahedral holes, would have to be transferred to
tetrahedral ones, with a loss in LFSE (see Table 2),
while Mn2+ ions, which have no LFSE in either en-
vironment, would have to be shifted from tetrahedral
to octahedral holes. Thus, the overall result would
Figure 1 3. Relative ionic radii of the divalent ions of the first transition ser- be a loss of LFSE, and inversion does not occur. For
ies. The Cr2 ! and Cu2 T points are somewhat uncertain because of the
distorted octahedra in which these ions are found.
Co304, 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-
The occurrence of the two “festoons” is a consequence hedral ones, and, again, it does not occur. For Fe304,
of the d electron configurations. We recall that the
however, the inversion is favorable insofar as LFSE
t2g electrons are nonbonding electrons (at least to a
first approximation) while the e„ electrons are anti- goes, since transfer of high-spin d6 Fe3+ from octahedral
to tetrahedral holes carries no penalty, while transfer
bonding; that is, their presence tends to weaken and of high-spin d6 Fe2+ from tetrahedral to octahedral
thus lengthen the metal ligand bonds. We therefore
holes produces a net gain in LFSE.
expect the metal ligand bond lengths to be little af- Still another example is provided by NiAl204, which
fected by the presence of t.2g electrons, but to be fairly
is inverse. Here transfer of Al3+ does not change the
sensitive to the presence of eg electrons, lengthening
net LFSE, but transfer of Ni2+ from the tetrahedral to
in proportion to the number of such electrons.
the octahedral holes is strongly favored.
In Figure 13, a smooth curve has been drawn through
It should be emphasized that these inversions could
the points for the d°, d:\ and dw ions. This curve may
not have been predicted ah initio, since this would re-
be considered to indicate the expected radii for ions
quire more detailed understanding of all the energy
having electrons equally distributed among all the d terms than was, or still is, generally available; but
orbitals, as do the da (all orbitals empty), d8 (all
orbitals half-filled), and d10 (all orbitals completely given the empirical fact that the normal and inverse
structures are similar in stability in the absence of
filled) ions. Thus, for Ti2+, the d2 ion, this would be LFSE effects, we have very good indications of where
the radius if it had 4/6 electron in the e„ orbitals;
and where not to expect inverse structures to occur.
actually the d2 ion has no electron at all in the e„
orbitals, the bonds to the ligands are therefore shorter Visible Spectra of Transition Metal Compounds
and the radius of the ion is taken to be less than the
value indicated by the curve. For the d3 ion, V2+, the Surely one of the most striking characteristics of the
transition elements is the fact that nearly all of their
actual number of eg electrons is 6/5 less than the number
compounds are colored and the colors are extremely
corresponding to the curve and the actual radius is varied. Even at the introductory level'—perhaps
again, and even more markedly, less than that in-
dicated by the curve. In the next two ions, which especially at this level—an attempt to explain this, at
least in correct qualitative fashion, would be worth-
have t2gzeg and t2g:iegl configurations, the number of
while and interesting to the students. Such an ex-
eg electrons increases and reaches the value correspond-
In the second half of the group, planation provides a good opportunity to correlate
ing to the curve. what may be isolated ideas in the student’s minds, for
the same sequence of configurations recurs, super-
example, the relationship between the color of a sub-
posed on the t2g%eg2 configuration reached at Mn!+, and
the second festoon thereby results. 11
A help in visualizing these structures may be the use of
The second striking structural result of d orbital models such as those described by Lambert, J. L., J. Chem.,
splitting is found (10) among the class of compounds Educ.,41,41 (1964).

Volume 41, Number 9, September 1964 j 473

stance and the positions of its absorption bands, and red light; it transmits only blue-purple light and a
the relationships of these in turn to the transitions little red light.
between electronic energy levels. The spectra of [Ni(H20)6]2+ and [Ni en3]2+ illustrate
There are however limitations on what can be done, the basis of the spectrochemical series of ligands. Since
since a complete understanding of the electronic states the energies of the absorption bands of Ni2+ in its com-
of the multi-electron ions, d2-d8, requires far more dis- plexes are proportional to the splitting of the d orbitals
cussion than would seem feasible in the usual introduc- by the ligands, it is evident that the electrons on the
tory course devoted to a comprehensive survey of six nitrogen atoms provided by the three ethylenedi-
chemistry. In the following paragraphs, the sort of amine molecules interact more strongly with the d
coverage which seems to this writer to be feasible is orbitals and hence cause a greater energy difference
outlined. between the e0 and 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-
Pur- Or -
mon occurrence, replacement of 2n H20’s by n ethylene-
B Iu e Yel low Red
pIe diamines causes the absorption bands to shift to higher
energies (shorter wavelengths). Moreover, a rather
Wave-Length, Angstroms long list of ligands can be arranged in the order of the
4000 5000 6000 7000
energies of the absorption bands for any given ion and
it is then found that this same order, with, at most,

-Visible Region

Wave -
Lengt h , A ng s troms
2000 4000 6000 8000 10000 1200

Frequency, cm*
Figure 1 4. The visible absorption spectrum of [TitHaOlfl]3 +.

The spectra of d1 ions can be covered without diffi-

culty. For a d1 ion in a regular octahedral field, the
[Ti(H20)6]3+ ion is a good example; its spectrum,
shown in Figure 14, consists of only one band centered
at about 20,000 cm-1 (5000 A). This can be identified
Figure 15. The electronic spectra of [Ni{H20)e]2 + (-) and [Ni ena]2 +
as arising from excitation of the electron from the to
{------), A "color map" of the visible region is also given.
the orbitals, and its energy corresponds to A0. Thus,
from the spectrum we are able to determine that A0 is
20,000 cm-’ or 57.2 kcal/mole.’2 The pale, red-purple only slight and occasional deviations, is obtained for all
color of the [Ti(H20)6]3+ ion is due to the fact that this the common transition metal ions. This ordering of
so placed as to allow most of the ligands is called the spectrochemical series, and is as
absorption band is
red light and some of the blue light to pass through follows, for some of the more familiar ligands:
unabsorbed and the combination of these two trans- I- < Br- < Cl- < H>0 ~
many other oxygen Uganda <
mission bands produces the red-purple color we see. NH3 ~
many nitrogen ligands < en < CN”
Figure 14 also shows where the principal colors occur The existence of such a consistent order of d orbital
in the visible spectrum, which extends, approximately,
splittings would not necessarily have been predicted
from 4000 to 7500 A. theoretically, but it is plausible. It is of considerable
Another good example, which can be demonstrated value in understanding, correlating and interpreting
easily, of the relationship between color and spectrum many observable changes which occur when ligands
is provided by the Ni2+ ion. In a pale green solution of are added to solutions of transition metal ions.
nickel sulfate in water, the color is caused by For metal ions with more than one d electron, de-
[Ni(H20)6]2+ ions. On adding ethylenediamine, the tailed explanation of the observed absorption bands
color turns deep blue, because of the formation of the seems beyond the scope of an introductory course.
[Ni ens]2+ ion. The spectra of these two solutions are For such ions, there are more than two ways (con-
shown in Figure 15. Again a “eolor map” of the
figurations) of arranging the d electrons in the orbitals
visible region is given. It is easily seen that and each of these configurations gives rise to more than
[Ni(H20)6]2+ has a minimum in its absorption where one energy state, because the electrons interact with
green light occurs, but absorbs nearly all the res" of the one another in various ways, as well as with the nucleus
light seen by the eye; hence it appears green. and with the ligands. Perhaps the nickel(II) ion can
[Ni en3]2+, on the other hand absorbs green light be used to illustrate, though not explain, the nature of
strongly and also yellow, orange, some blue and some this rather complex situation.
There are three possible configurations for eight d
12
For converting spectral energies in their usual units of cm-1 electrons in an octahedral ligand field: f2/e92 (most
to chemical energies in their usual units of kcal/mole, the con-
version factor is: 350 cm-1 I kcai/moie. Recall that
= stable), <2ff5e93 (next most stable), and (least
energy (per mole) Nhv Nhc/\.
= =
stable). When all of the possibilities for interaction

474 / Journal of Chemical Education

between the electrons are considered it is found that Epilogue
the f2(76ef2 configuration gives rise to one state with two With due acknowledgment to G. B. Shaw for the
unpaired electrons, which is most stable, but also to inspiration, it might be said that theories of chemical
two other states in which the two es electrons have their
bonding—neglecting not a few which are entirely value-
spins opposed. The ttfe/ configuration gives rise to less—fall into one of two categories: those which are too
four states, two of which have two unpaired electron
good to be true and those which are too true to be good.
spins. The highest energy configuration, f2ff4ef4, gives “True” in this context is intended to mean “having
rise to four states, only one of which has two unpaired
electron spins. Since there is a general rule in molecu- physical validity” and “good” to mean “providing use-
lar quantum mechanics that significant absorption of ful results, especially quantitative ones, with a relatively
small amount of computational effort.” The proper,
light can occur only when the resulting transition of
electrons takes place without change in the number of rigorous wave equation for any molecular situation
unpaired electron spins, the appearance of just three represents a theory of that situation which is too true
to be good. Most theories which are too good to be
absorption bands in the spectra of octahedrally co-
ordinated Ni2+ ions is easily understood. The transi- true are those in which the real problem per se is not
tions are from the state of the f2/es2 configuration with treated, but rather an artificial analogue to the real
two unpaired electrons to the two states of the problem, contrived so as to make the mathematics
configuration with two unpaired electrons and to the tractable, is set up and solved.
one state of the f2/e„4 configuration which has two The electrostatic crystal field theory, using the point
unpaired electrons. charge approximation, is such a theory—at its best, or,

Volume 41. Number 9, September 1964 / 475

 A Selected Annotated Bibliography

Essentially Nonmathematical Comprehensive Accounts

Cotton, F. A., and Wilkinson, G., “Advanced Inorganic Chem- 1963. Chapter 8. Recapitulates in contemporary notation
istry, A Comprehensive Text,” Interscience, New York, and more didactically the basic symmetry considerations first
1962. Chapter 26 gives a general account of LFT suitable expounded by Bethe. Also gives an introduction to the inter-
for undergraduate students, though probably not for the pretation of polarized spectra.
average freshman without supplementary material. Chapter Thermodynamic Consequences of LFT. George, P., and
29 on the elements of the first transition series discusses the McClure, D. S., “Progress in Inorganic Chemistry,” Vol. 1,
electronic structures of many compounds and complexes in F. A. Cotton, Editor, Interscience, New York, 1959, p 381.
terms of LFT. This is still the definitive article on the subject. It is both lucid
Orqel, L. E,, “An Introduction to Transition Metal Chemistry, and thorough.
Ligand Field Theory,” John Wiley, New York, 1960. Covers Paramagnetic Resonance. Low, W., “Paramagnetic Resonance
virtually all aspects of LFT in a lucidly nonmathematical in Solids,” Academic Press, New York, 1960. Tightly written
way. Suitable for most undergraduates, but the average and thorough. Develops LFT as it is needed for interpreta-
freshman will need assistance. tion of electron spin resonance (ESR) data and reviews the
Dunn, T. M,, in “Modern Coordination Chemistry,” J. Lewis ESR literature in detail.
and R. G. Wilkins, Editors, Interscience, New York, 1958. Kinetics and Mechanism. Basolo, F., and Pearson, R. G.,
A superb treatment, though more sophisticated than either “Mechanisms of Inorganic Reactions,” John Wiley, New York,
of the two preceeding ones. 1958. Gives a thorough discussion of the bearing of LFT on
Sutton, L. E., J. Chem., Educ., 37, 498 (1960). Informative interpretation of kinetic data for reactions of complexes.
short resume. Pearson, R. G. J. Chem. Educ., 38,164(1961). Gives a more
Pearson, R. G., Rec. Chem. Prog. 23, 53 (1962). Informative recent brief outline.
short r6sumd. Structural Consequences of LFT. Dunitz, J. D., and Orgel, L.
E., “Advances in Inorganic and Radiochemistry,” Vol. 2, H. J.
Mathematical Comprehensive Accounts EmelIsus and A. G. Sharpe, Editors, Academic Press, New
Ballhausen, C. J., “Introduction to Ligand Field Theory,” York, 1960, p. 1. Good summary and explanation of the use
of LFT to interpret what are presumably Jahn-Teller effects in
McGraw-Hill, New York, 1962. A mathematical develop- the structures of transition metal compounds, as well as other
ment which begins at a point appropriate for any graduate
structural phenomena.
chemist with some knowledge of quantum theory in general
Molecular Orbital Theory. Gray, H. B., J. Chem. Educ,, 41,
and the Slater-Condon theory of atoms in particular (the
2 (1964). An explanation of the MO treatment of complexes
summary account of which, in Chapter 2, is more a recapitula- in its simple LCAO form and a survey of results.
tion than an introduction). It develops all principal aspects
of the subject assuming only the normal chemist’s training and Paramagnetic Resonance. Carrington, A., and Longuet-
ability in mathematics. It concludes with an excellent review Higgins, H. C., Quart. Rev., 14, 427 (I960). A lucid, quali-
of the experimental data on spectra and magnetism. An tative introduction.
excellent book for the serious student. Magnetism. Lewis, J., and Figgis, B. N., “Progress in Inorganic
Griffith, J. S., “The Theory of Transition Metal Ions,” Cam- Chemistry,” Vol. 6, F. A, Cotton, Editor, Interscience, New
bridge Univ. Press, Cambridge, England, 1961. An elegant
York, 1964. The best and most timely exposition of theory
and fact for the inorganic and physical chemist.
book, but very sophisticated. Primarily for those with a
Nephelauxetic Effects. Jorgenson, C. K., “Progress in Inorganic
strong background in physics and mathematics and a desire
to go very deeply into the theory. Chemistry,” Vol. 4, F. A. Cotton, Editor, Interscience, New
York, 1962, p. 73. A mine of useful data, analyzed in depth.
Articles Covers everything from the general idea to the controversial
or Monographs on Special Topics fine points.
Group Theoretical Basis of LFT. Cotton, F. A., “Chemical Optical Rotatory Dispersion. Woldbye, F., Rec. Chem. Progr.,
Applications of Group Theory,” Interscience, New York, 24, 197 (1963). An excellent introduction to theory and facts.

Volume 41. Number 9, September 1964 / 475

perhaps, at 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 “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. Physik., 58,205 (1929).
willing to perpetrate a deliberate and conscious de- (2) Bethe, H., Ann. Physik [5], 3, 135 (1929).
ception. Naturally, it has long been recognized that (3) Ballhauken, C. J., Kgl. Danske Videnskab. 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- (4) The qualitative argument given here is based on the calcu-
lations of Kleiner, W. H., J. Chem. Phys., 20, 1784
plexes and crystals which took no account at all of (1952) and Freeman, A. J., and Watson, R. E., Phys.
covalent character in the metal-ligand bonds was not Rev., 120, 1254 (1960).
entirely correct. But it was generally assumed that (5) J0RGENSEN, C. K., PAPPALARDO, R-, AND SCHMIDTKE,
the electrostatic approach was partially or qualitatively, H.-H., J. Chem. Phys., 39, 1422 (1963).
perhaps, in some cases, even semiquantitatively valid, (6) Alei, M., Jr., Inorg. Chem., 3, 44 (1964).
and thus perfectly legitimate for use at least as a first (7) Sugano, S., and Shulman, R. G., Phys. Rev., 130, 517
(1963) .

approximation, or as a half truth which further study (8) Hush, N. S., and Pryce, N. H. L., J. Chem. Phys., 28,
would not contradict, but merely qualify and enlarge 244(1958).
upon, I believe that most teachers at some time find it (9) Blake, A. B., and Cotton, F. A., Inorg. C'hem., 3, 5
(1964)
necessary to use the general approach of beginning a
.

(10) McClure, D, S., Phys. Chem. Solids, 3, 311 (1957); Du-

topic with a facile half truth and that this is fair prac- nitz, J. D., and Orgel, L. £., Phys. Chem. Solids, 3,
tice. I do not believe, however, that it is ever justified 318(1957).

Qualitative Organic (?) Chemistry

In certain chemistry building there are five labs, all in a row, each painted a different color
a
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 sufficient to 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 (III) 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(III) chloride solution is kept in the lab next to the lab with the sublimation furnace.
Tollens reagent is in the same lab as the chloroform.
Lucas keeps the supply of Lucas reagent.
Friedel works next to the blue lab.
Submitted by Prof. James G. Traynham
Louisiana State University
Baton Rouge

476 / Journo/ of Chemical Education