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Resource Papers-I

-
Prepored under the sponsorship of
The Advisory Council on College Chemistry

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

The presentation of ligand field theory in causes, but for most undergraduate courseeand cer-
the first college ehemistry course cannot be said to be tainly for the introductory course--such rigor and wm-
essential. If time is limited, or if the ability of the prehensiveness are unnecessary.
students and/or their interest in chemistry as a pure
science rather than as a branch of useful knowledge are Causes of Inner Orbital Spitting$
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 sigxZ6oantly split when an ion is placed in a
is time enough in later years of the chemistry cur- chemical environment was fist 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 a t any (electrostatic, or covalent, as discussed presently)
level. I t 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 dw,
teacher, first, an awareness and understanding of the d, and dvz orbitals remain equivalent, as do d ~ * - and~ %dis
dangers and, sewnd, the possession of some concrete orbit&.
ideas about how to avoid them. This article presents In square surroundings, the drz and 6.orbitale remain equiva-
an outline of ligand field theory in its present state and imr, but the d,,, d,,-,I and d.1 orb~talssrenot equivalent toany
a t an introductory level; it suggests, partly in precept othem.
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 wncern 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 Adviaory Council on College Chemistry
the origins and (2) the consequences of the splitting of aa one of the activities of the Teaching Aids Panel. The
inner orbitals of ions by their surroundings in chemical Advisory Council on College Chemistry (ACI)is supported
compounds. In this article we shall restrict attention by the National ScienceFoundation. Profeasor Charles C.
primarily to penultimate d orbitals, i.e., the 3d orbitals Price, of the University of Pennsylvania, Philadelphia,
Penna. 19104, ia the chairman.
for ions of the first transition series, 4d and 5d orbitals
for ions of the sewnd and third transition series. To a Single copy reprinta of this paper are being sent to
ohemiatry department chairmen of every US.institution
considerable degree, it is possible to deal with the two offering college ehemistry coumes and to others on the mail-
parts of ligand field theory separately; this has the im- ing list for the AC1 Newsletter. Additional single copies
portant consequence that many of the significant and will be sent free to d l interested individuals who make
relatively straightforward results of d-arbital splittings, request to the Editor of the AC1 Newsletter:
e.g., ligand field stabilization energies, stereochemical Professor E. L. Haenisoh
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 &&cult and Multiple copy orders (in lota of.110) 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 discurnion of all the wnse- Orders m s t be add~essedto Professor H m i s c h , mt to the
quenoes of inner orbital splittimgs could not be given Jozmml of Chemieol Educatiun.
without intimately interweaving an examination of the

466 / Journol of Chemical Education


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 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 diierent ways. atoms? 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 orhitals, even From the theoretical side, the inadequacy of the
if intrinsically similar, are diierently 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 (4). 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 offereda n 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 essatially a point,
has often been considered to represent the chemist's surrounded by a spherical cloud of total charge 10e, -
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, a n electron in an orbital whose lohes complex ion or in a MF, salt.
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 Ociohedral Tetrohedrol Square
of a series of inherently similar orbitals will vary in- Figure 6.Orbital rpliwing diagrams for the Ihree most important types of
versely according to the extent to which they bring complex. Orbitals within each pair of bracer are of identical stobilily.
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
he 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., AO 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 t~ the wave function above. Using this qualitatively realistic representa-
for the d orbitals. I n relatively recent times, Ball- tion of the physical situation, the following argument
hausen (5) showed that if these parameters are assumed may be developed.
to have the same values in an octahedral complex,
MX6 and a corresponding tetrahedral one, MX,, The evidence will not be reviewed here. Several snmmeries
the ratio of A , to A. will be v9. It has also been shown are cited in the bibliogmphy. Those in ORGEL,BALLHAUSEN,
and C o m AND ~ WILKINSON me especirtlly recommended.
that the absolute values of A. (or A 3 can be obtained
0 To more deeply buried eleotrons of a cation, a near neighbor
withm a factor of less than two by choosing reasonable anion may come closer to appearing as a point negative oharge.
values for the various parameters required. Recall in this connection s, basic theorem of eleotrosts.tim, due to
However, in spite of all this sort of pragmatic success, Gauss, which st&^ that if a tmt 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 r a n earth ions, calcula-
both experimentally and theoretically. The experi- tions of orbital splittings using the paint 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 (6) to show that here, too, covalence playa 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 eomputatian of the electrostatic effect produced
'When an orbital wave function is expressed in sphericd by an array of ions in a crystal which lie outside of the firat co-
coordinatee $(7, a, 9) = R(r)B(B)@(4), the radial part is the I2(r). ordination shell of the cation being treated. Even for second
The parameter r measurea the radial distance from the origin. nearest neighbors, however, some significant covalence effect,
The angulss psst of the wave function is B(B)*(+)which involvea or orbital werlap, 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 I7O in
angles 8 and 4. the ion pair or "outer sphere complex!'

468 / Journal of Chemicol Education


An electron occupying a n orbital which has lobes dominantly the characteristics of the lower energy
such as A and A' in Figure 7, directed a t 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 86. However, if the two atomic orbitals (a, r 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 band, 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.

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. (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
an electron occupying an orbital which has lobes, such oppmpriote ligond orbitals in octahedral mmplexes.
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
(01 (bl
slightly in favor of orbital A . Actual calculations, using
Figure 9. Sketch showing the lack of interaction between o o orbit01 (ruch
realistic ( e . , Hartree-Fock) orbitals for metal and as o Isorbital of a metol ion1 ond a ligand *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
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- 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
rate calculations are made (very elaborate, unfor- 10".
tunately), almost quantitatively correct results can
be obtained (7).
Now it can be seen that by considering the overlap
It is not very difticult to see, a t least qualitatively, of orbitals, we have arrived a t 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 (ax, a2, Fig. 8a), and these atoms approach split in an octahedral environment, so that the e,
to withim a few Angstroms of one another, the orbitals
orbitals become less stable than the h, orbitals. For
become mixed to form two new orbitals, one, (as), 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, ( a d , ordering of the orbitals; the actual magnitude of the
having relatively low amplitude (low electron concentr&
tion) between the nuclei. When electrons occupy '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 symbok and character
(an antibondimg orbital) a repulsive or antibonding tables to describe molecular symmetry. The e implies s. two-
force is set up. Furthermore, if the two atomic dimensional representation, t, a. three-dimensional represent%-
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 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 effect^,'^ are probably best omitted. In the following
In order to predict or explain magnetic properties paragraphs, the sort of coverage which might be given
of a transition metal ion in its complexes or other to a few themnochemical 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 d i 5 lowing part of this section.
cussion may then proceed to higher levels of sophistica- The derivation of ligand field stabilization energies
tion if desired, hut 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 e, orbitals lie s/5A above
first. and the t2, orbitals 2/0A below the energy which all
By referring to the electron coniiguration diagrams the d orbitals would have if they were surrounded by
in Figure 11, we see first of all that for dl, d2, da, d3, 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
always be 1,2,3,2,or 1 unpaired electrons, respectively, over a sphere instead of wncentrated into six equal
no matter how great the value of AO may b e ~ o m e . ~ amounts a t the vertices of the octahdemn. This
Deviations from these numbers in the dZ, d3 or d8 raising and lowering of the energy of the sets of orbitals
cases (provided i t is certain they are not due to any by amounts inversely proportional to their degeneracies
intermolecular etrects) can he 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, dd d6, and d' 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- tiigs 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 & relative to P for ligaud 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 e, orbits (see Fig. 10). A discussion of
giving the low-spin configuration produce A values in ligand field stahilization 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 A, than that of the &, 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+), TiZ+, VZ+,. . . Ni2+, CuZ+, Zn2+
just described are correct. For instance, for the d" (Sc2+is in parentheses because it has not actually been
configuration of Coa+,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 [CoFs13-, the A. value is only about 37 from the dO to the dlQion for the complexes or com-
kcal/mole, while in [CO(NHs)a13+ AO is about 66 pounds with a particular ligand or anion. This is
kcal/mole. In agreement with these facts, [CoF6Ia- because we expect a fairly smooth variation in the
has four unpaired electrons, while [CO(NH~)~]'+ has energy of each type of orbital and hence of the over-
none. For the d6 configuration in the Fez+ ion, the all energy of formation, provided all the orbitals are
pairing energy is about 40 kcal/mole, while the A. either equally occupied in each case or the population
value in [Fe(NH&12+ is only about 35 kcal/mole. increases uniformly. Now for all the orbitals except
Therefore [Fe(NHa)slz+ unlike [Co(NH3)6J3+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 - l i e orbitals) whose
Ligond Field Stabilization Energies separate populations do not increase uniformly. The
The fact that for most of the d" configurations the e , 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 vlo = electron
probability, but instead tend to occupy three of them a t each step. Similarly, a uniform increase in the
in preference to the other two in an octahedral field population of the t2, orbitals would mean an increase
(or two in preference to the other three in a tetrahedral of 6/10 = 3/6 electron a t each step. On this basis,
one) has both energetic and structural consequences. the figures for the "uniform" e , and tZ, populations
Some of these are sufficiently straightforward that shown in Table 1 are obtained. Below them are the
they can probably he 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 #, d6, and
dlQcases the "uniform" and the actual populations are
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. P - 1 s or give a greater fraction of the total electron density
dm-'p configuration, which might have a. Merent number of un- in less stable e, orbitals and a smaller fraction in the
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. '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 mental points for the do, dS, and dlo 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 &like orbitals.
and the actual configurations. This is only a first approximation, however, since there
For the dl case, to go from the uniform to the actual are other effects, such as the non-uniform variation of
configuration, 2/6 electron is transferred from the e, ionic radii, to be discussed shortly, which must be
to the tz, orbitals. There is thus a stability increase considered; these effects are not believed to be large
(energy decrease) of 2/6An. Again, for the d' case, (8).
, .
electron is transferred from e, to t,, orbitals, caus- Similar results are obtained for lattice energies and
ing an increase of 4/sAo 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 An 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 Liaand Fields be deduced. These are also given in Table 2.
No. of -LFSE'-
electrons Oct 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-
I I I I I I I I I I I
dration, as given by the reaction: Ca Se T i V Cr Mn Fe Co Ni Cu Zn
M"(g) + mH2O (1) = [M(HsO)OI'+(aq) Figure 12. Hydrotbn energies of divalent ions of the flmt trransikn series.
Solid circler are experimental volver; open circles are obtained b y sub-
for all the known dipositive ions of the first transition bacting the calculated LFSE'r from the experimental voluer.
series. 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 ( 1 3 0 kcal/mole) of the total energies (60& 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,
(Ca2+, do; Mu2+, d5; and Zn2+, dln) which do, in fact, whereas Ni2+ especially and also Cu2+ seem defi-
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+ (d") 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, dO, d6, dln they continue to be so distributed in LFSE, while with Ni2+we have the largest octahedral
the [M(HzO)a12+ ions; in the remaining cases, they LFSE together with an average tetrahedral LFSE.
move completely or more completely to the more For Cu2+the octahedral LFSE also exceeds the tetra-
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
z a t i a energies, LFSE's. If the values of An are known octahedral and tetrahedral complexes requires caution
(as they are from spectral data, see later) the LFSE's in pressing the LFSE argument. It has recently been
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- [MCL12+(g) + 6 H*O (g) = [M(Hdl)s12+(g) + 4 C1- (9)
472 / Journal of Chemical Education
Some Stereochemical Consequences called spinels. These are oxides whose most general
There are two striking examples of the effect of d formula is ABC04, where A, B and C are cations, the
orbital splittings ou stereochemistry which can r e a sum of whose charges is +8. I n many cases, such as
sonahly be covered in a discussion of LFT a t the the mineral spinel, MgAh04, which gives its name to
introductory level. the class, B = C , and in still others, all the cations have
The first is the irregular variation in the radii of the same atomic number, e.g., FeaOd, MnnOi and CoaOa.
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 ~ n ~ c u ptctrah~drsl
v i ~ ~ ~ iittcrsticc.; and the r e ~ l ~ n i utwo
i~~g
ions would be expected to show an overall decrease thirdsoc~:~~pyingoctnhair~lintersticcs.~~ 'll~c~mmnal"
since the nuclear charge is increased through the spinel structure, when the charges on the ions are +2,
series, while the 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 he shown
radii is observed, hut, 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 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
cozt sZ+T ~ +~ n ? +~ e " co2+ N ? + C U ~ + z$+
~ ~ + VcrZt to octahedral holes. Thus, the overall result would
Figure 13. Relative ionic rodii of the divalent ions of theflrrt transition rer- he a loss of LFSE, and inversion does not occur. For
ier The Cr2+ cmd Cv2+ points are somewhat uncertain becawe of the Co301, inversion would be extremely disfavored, due
d~rtortedoctohedro in which these ions o r e found.
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 Fea04,
of the d electron configurations. We recall that the
however, the inversion is favorable insofar as LFSE
tRo electrons are nonbonding electrons (at least to a goes, since transfer of high-spin d6Fea+from octahedral
first approximation) while the e, electrons are anti-
to tetrahedral holes carries no penalty, while transfer
bonding; that is, their presence tends to weaken and
of high-spin d6 Fez+ from tetrahedral to octahedral
thus lengthen the metal ligaud bonds. We therefore holes produces a net gain in LFSE.
expect the metal ligaud bond lengths to be little af-
Still another example is provided by NiA1104,which
fected by the presence of k o electrons, hut to he fairly
is inverse. Here transfer of AIS+does not change the
sensitive to the presence of e, electrons, lengthening
net LFSE, hut 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 dO, d5, and dlo ions. This curve may not have been predicted ab 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; hut
orbitals, as do the d? (all orbitals empty), d5 (all
given the empirical fact that the normal and inverse
orbitals half-filled), and dlo (all orbitals completely structures are similar in stability in the absence of
filled) ions. Thus, for Tiz+, the dZion, this would be
the radius if it had v6
electron in the e, orbitals;
LFSE effects, we have very good indications of where
and where not to expect inverse structures to occur.
actually the d2 ion has no electron a t all in the e ,
orbitals, the bonds to the ligands are therefore shorter Visible Spectra of rransition Metal Compounds
and the radius of the ion is taken to be less than the
Surely one of the most striking characteristics of the
value indicated by the curve. For the d3 ion, VZ+,the
transition elements is the fact that nearly all of their
actual nuniber of e, electrons is 6/5 less than the number
conlpounds are colored and the colors are extremely
corresponding to the curve and the actual radius is
varied. Even a t the introductory level-perhaps
again, and even nmre markedly, less than that in-
especially a t this level-an attempt to explain this, a t
dicated by the curve. In the next two ions, which least in correct qualitative fashion, would be worth-
have t,,ae, and tlg3eC2configurations, the number of
while and interesting to the students. Such an ex-
e, electrons increases and reaches the value correspond-
planation provides a good opportunity to correlate
ing to the curve. I n the second half of the group,
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 t ~ , ~ configuration
e,~ reached a t MuZ+,and
the second festoon thereby results. " 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 LIMBERT.J. L., J. CHEM.,
splitting is found (10) among the class of compounds 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
red light: it transmits onlv blue-~umle
* light and a & -
little red iight.
between electronic energy levels. The spectra of [Ni(H20)612+and [Ni en#+ 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-dS, requires far more dis- ulexes are nro~ortionalto the s~littinzof the d orbitals
cussion than would seem feasible in the usual introduc- by the ligands, it is evident &at theelectrons on the
tory course devoted to a comprehensive survey of six nitrogen atoms provided by the three ethylenedi-
chemistry. I n 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
outlmed. 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
Wove-Length, Angstrom long list of ligands can be arranged in the order of the
4000
energies of the absorption bands for any given ion and
it is then found that this same order, with, at most,

Wave-Length, Angstroms
0
2000 4000 6000 8000 ioooo 1200
I I I I I
25.000 20.000 15,000
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 50000 25000 15000 10000 8000
Frequency, cm-'
a t about 20,000 cm-' (5000 A). This can be identified
as arising from excitation of the electron from the h, to Figure 15. The electronic spectra of [Ni(HnO1sl2+ 1-1 and [Ni en#+
( - - - - - - ) . A "color mop" of the visible region is olro given.
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 only slight and occasional deviations, is obtained for all
color of the [Ti(H20)#+ ion is due to the fact that this the common transition metal ions. This ordering of
absorption band is so placed as to allow most of the ligands is called the spectrochemical series, and is as
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-
mission bands produces the red-purple color we see.
Figure 14 also shows where the principal colon occur
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
in the visible spectrum, which extends, approximately, splittiugs 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 NiZ+ion. I n 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]z+ ions. On addmg 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]%+ ion. The spectra of these two solutions are For such ions, there are more than two ways (con-
shown in Figure 15. Again a "color 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(HzO)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(I1) ion can
[Ni en3I2+, 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 situatio~~.
There are three possible configurations for eight d
1% For converting spectral energies io their usual units of cm-I
to chemical energies in their usual units of koal/mole, the con-
electrons in an octahedral ligand field: tzO6eez (most
version factor is: 350 cm-' = 1 koal/mole. Recall that stable), hq6ee,3 (next most stable), and hO4e,' (least
energy (per mole) = Nhv = Nhc/X. stable). When all of the possibilities for interaction

474 / Journal o f Chemical Education


between the electrons are considered i t is found that Epilogue
the hO6eszconfiguration 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 e, electrons have their bonding-neglecting not a few which are entirely value-
spins opposed. The tz,5e,a configuration gives rise to l e s s f a l l 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 t m e to he good.
spins. The highest energy configuration, t2,4e,4, gves
"True" in this context is intended t o 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
light can occur only when the resulting transition of small amount of computational effort." The proper,
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
absorption bands in the spectra of octahedrally co- to be good. Most theories which are too good to be
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 tz,Be,2 configuration with treated, but rather an artificial analogue to the real
two unpaired electrons to the two states of the hs6e,s 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 tzC4ee,4configuration 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, Sedember 1964 / 475


A Selected Annotated Bibliography

Essentiolly Nonmofhemoficol Comprehensive Accounts


COTTON, F. A., AND WILKINSON, G.,"Advanced Inorganic Chem- 1963. Chapter 8. Recapitulates in wntemporary notation
istry, A Comprehensive Text," Intmcience, New York, and more didactically the basic symmetry considerations first
1962. Chapter 26 gives a. general account of LFT suitable expounded bv Bethe. Also an introduction to the inter-
for undergraduate students, though probably not for the pr&ation of polarized spectra:
average freshman without supplementary material. Chapter T h m d y n a m i c Crmwquences qf LFT. GEORGE, P., AND
29 on the elements of the first transition aeries discusses the MCCLTTRE, D. S., Progress in Inorganic Chemistry," 1701. 1,
electronic structures of many compounds and complexes in F. A. COTTON,Editor, Interscience, New York, 1959, p 381.
terms of LFT. Thirris still the definitive article on the subject. I t is bothlucid
ORGEL,L. E., "An Introduction to Transition Metal Chemistry, and thorough.
Ligand Field Theory," John Wiley, New York, 1960. Covers Pa~amapnefieResonance. Low, W., "Paramagnetic Resonance
virtudly all aspects of LFT in a. lucidly nonmsthematiesl 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 interprets-
freshman will need assistance. tian of electron suin 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, 1558. Kinetics and Mechanism. B a s o ~ o ,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 rkumi.. PEARSON, R. G. J. CHEM.EDUC.,38,164 (1961). Gives amore
PEARSON,R. G., Rec. Chem. Prog. 23, 53 (1962). Informative recent brief outline.
short r6snm6. Struclural Consequences of LFT. DUNITZ,J . D., AND ORGEL,L.
E., "Advances in Inorganic and Radiochemistry," Vol. 2, H. J .
Mathematical Comprehensive Accounts EMELOUSand A. G. SHARPE.Editors. Academic Press. New
BALLHAUSEN, C. J., '.Introduction to Ligand Field Thwry," r , 9 0 1. 1 Good suwrnary and e x p l ~ u ~ t i ~ m the uae
McGraw-Hill, New York, 1962. A mathematical develop- 01 I.FT 11, interpret wlut are prcsu~s.ublyJilln-Teller efler.ts i u
ment which begins a t a point appropriate for any graduate the struc tun.* of trmsit~onmet31 compounds, ns well n s other
chemist with some knowledge of quantum theory in general structural phenomena.
and the Slater-Condon theory of atoms in particular (the Molecula7 Orbital T h e w . GRAY,H. B., J. CHEM.EDUC.,41,
summary account of which, in Chapter 2, is more a meapitula- 2 (1964). An explanation of the MO treatment of complexes
tion than an introduction). It develops all principal aspects in its simple LCAO fonn and a snrvev of results.
of the subject assuming only the normal chemist's training and ~aramagne& Resonance. CARRINGTON, A,, AND LONGUET-
ability in mathematics. It concludes with an excellent review HIGGINS,H. C., Qumt. Rev., 14, 427 (1960). A lucid, quali-
of the experimental data an spectra and magnetism. An tative introduction.
excellent book for the serious student. .11ngnd,~rn I.I:WIS,.I., .ASD FIGGIS, n. S . ,"I'rope~s ih I u w ~ m i v
GRIFFITH,J. S., "The Theory of Transition Metal Ions," Cam. U1eni19rr?.,"Vd. 6 , F. .\. (.'OTMN,Editor, Interarience, Sen.
bridge Univ. Press, Cambridge, England, 1961. An elegant l ork, 1964. 'l'1.e best nrrd most tirrwly expodion of theory
book, but uery sophisticated. Primarily for those with s and fact for the inorganic and physical chemist.
strong background in phyaics and mathematics and a desire NephelauzeticEffects. JYIRGENBON, C. K., "Progress in Inorganic
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 or Monographs on Speciol Topics Covers everything from the general idea to the controversial
fine points.
Group Theoretical Basis of LFT. COTTON,F. A,, "Chemical Optical Rotatory Dispersion. WOLDBYE, F., Ree. Chem. Pmgr.,
Applications of Group Theory," Interscience, New York, 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