First transition element (except Sc+2 which is unstable) are plotted as a function of atomic

number. If one substracts the predicted CFSE from the experiment enthalpies, the resulting
points lie very nearly on a straight line from Ca+2 to Zn+2 and Sc+3 to Fe+3(the +3 oxidation
state is unstable in water for the remainder of the first transition series). Many
thermodynamic data for coordination compounds follow this pattern. In each case the
double-humped curve can be ascribed to CFSE.

A slightly different from of the typical two-humped curve is shown by the ionic radii of the
3d divalent metals. For both dipositive and tripositive ions there is a steady decrease in
radius for the strong field case until the . Configuration is reached. At this point the next
electron enters the e level, into an orbital directed at the ligands, repelling them and
causing an increase in the effective radius of the metal. In the case of high-spin ions the
increase in radius occurs with the t, e configuration for the same reason.

The same effect can be seen from a sinle series of complexes formed with the ligand
N(CH2CH2N=CHC3H4N)3 . the geometry of the complexes formed with this ligand is discussed
in some detail in chapter 10, but for now we may note that six of the nitrogen atoms
coordinate to the metal in a approximately octahedral arrangement and are thus directed
toward the e orbitals. The seventh nitrogen atom is located in the center of an octahedral
face(axial coordination) and thus interacts most directly with a x orbital. The shorter
distances represent the lengths of the octahedral bonds. The six bonds of this type in a
complex are not identical in length (hence the two values shown for each compound), but
the slight difference is not important for the present discussion and may be ignored. The
longer axial bond in each complex represents the distance to the seventh nitrogen atom.
There are several effects to be seen in this series:

(1) There is a general decrease in size progressing across the series, to be expected
from the usual decrease in size across a series.
(2) An increase in electrons in orbitals directed at the nitrogen atoms causes an
increase in bond length, both for the e orbitals (octahedral nitrogen atoms) and the
t orbitals (axial nitrogen atom).
(3) Specifically, in the case of the Fe+2 complex, the only low-spin complex in the series,
there is a dramatic decrease in one distance and a concomitan increase in the other.
The low spin t configuration maximizes electron density toward the axial nitrogen
atom while minimizing t in the direction of the octahedral nitrogen atoms.
Further evidence of the importance of CFSE comes from the stability of particular oxidation
states. In aqueous solution Co(III) is unstable with respect to reduction by water to form
Co(II). Althought there are several energy terms involved, this may be viewed as a
reflectiom of the high third ionization energy of cobalt. If various moderate to strong field
liands are present in the solution, however, the Co(III) ion is perfectly stable; in fact, in some
cases it is difficult or impossible to prevent the spontaneous transformation of Co(II) to
Co(III)

For example, the appropriate oxidation emfs are:

[Co(H2O)6]+2 [Co(H2O)6]+3 +e 0 = -1.84 (9.13)

[Co(EDTA)]-2 [Co(EDTA)6]- +e 0 = -0.60 (9.14)

[Co(ox)3]-4 [Co(OX)3]-3 +e 0 = -0.57 (9.15)

[Co(phen)3]+2 [Co(phen)3]+3 +e 0 = -0.42 (9.16)

[Co(NH3)6]+2 [Co(NH3)6]+3 +e 0 = -0.10 (9.17)

[Co(en)3]+2 [Co(EN)3]+3 +e 0 = +0.26 (9.18)

[Co(CN)5]-3 + CN- [Co(CN)6]-3 +e 0 = +0.83 (9.19)

Note that the order of ligands in Eqs. 9.13-9.19 is approximately that of the spectrochemical
series and, hence, that of increasing crystal field stabilization energies. The oxidation of
Co(II) to Co(III) result is in a change from high to low spin. We think of the oxidation as
taking place in two steps, the first being rearrangement of electrons to the low-spin state
and the second the removal of the seventh electron to produce Co(III):
3 2 6 1 6 0
CoII(t2ge) CoIII(t2ge) CoIII(t2ge)

This is not to imply that the reaction actually occurs in this manner but that we may
consider the thermodynamics as the sum of the hypothetical sequence. Now the first step
involves the pairing of electrons and the pairing energy will be in part compensated for by
the extra CFSE of the low-spin configuration (18 Dq to 24 Dq). The stronger the field, the
larger the valueof Dq. It should be pointed out that CFSE is only one of a number of factors
affecting the emf. In particular, entropy effect is associated with chelate rings can be
important and are largely responsible for the fact that the order of ligands in Eqs. 9.13-9.19
is different from that of the spectrochemical series.

Further evidence will be presented later to indicate the adventages of considering

coordination compounds in terms of splitting of d orbital degeneracy, but one more simple
example will be presented here to conclude this discussion. It is possible to study the
spectra and magnetic properties of coordination compounds under pressures of as much as
1.5 x 1010 Pa. Althought the strong repulsive forces of the atoms prevent much compression,
the results are exactly what we wuld expect as a result of the ligands beomh pushed closer
to the metal and interacting more strongly with the d orbitals of the latter. The spectra are
thus altered with the absorption maxima shifted toward the blue or high-energy end of the
spectra. The magnitude of separation of the energy levels. 10 Dq, is correspondingly
increased. The increase in 10 Dq, the rate of increase with distance (proportional to r-5), and
he increase in integrated intensity (proportional to r-8)are al in reasonably good agreement
with a crystal field perturbation of the d orbitals.

Octahedral versus tetrahedral coordination

Thus far we have discussed three types of complexes: high-spin octahedral, low-spin
octahedral, and high-spin tetrahedral. For the first transition series large numbers of each
type of complex are known, together with some complexes of the geometries to be
considered later. There are several factors that influence the adoption of tetrahedral or
octahedral coordination, and occasionally the balance between opposing factors is a
delicate one.