You are on page 1of 2

Information Textbooks Media Resources

A Common Inorganic Chemistry Textbook Mistake:


Incorrect Use of Pairing Energy in Crystal Field
Stabilization Energy Expressions
David Tudela
Departamento de Qumica Inorgnica, Universidad Autnoma de Madrid, 28049-Madrid, Spain

Crystal field theory (CFT) is a purely electrostatic approach As a result of the splitting of the d orbitals, there is a crystal
to the bonding in transition metal complexes. It considers field stabilization energy (CFSE) relative to the hypothetical
the effect of the electric field created by the ligands (taken as spherical field with no splitting. Each electron in a t 2g or-
negative point charges) on the energy of the metal ion d bital lowers the energy of the system by 0.4 o, whereas each
orbitals. Although it is a rough approximation, CFT gives electron in an eg orbital raises the energy by 0.6o. In addi-
satisfactory results, and because of its simplicity, it is easily tion, each electron pair forced to be paired in the same or-
understood by undergraduate students. Furthermore, CFT is a bital raises the energy of the system by the pairing energy P.
good introduction to more sophisticated bonding theories. For d4, d5, d6, and d7 configurations, if o < P, the system is
When a transition metal ion is approached by a set of more stable if the electrons occupy the eg orbitals rather than
ligands, there is a large electrostatic attraction and the energy of being paired in the t2g orbitals, giving rise to high-spin
the system is lowered, so that the complex is stable. Although complexes. If o > P, a low-spin complex results in which the
the total energy of the system is lowered, the energy of the electrons are paired in the t 2g orbitals rather than occupying
metal ion d orbitals is increased by the electrostatic repulsion the higher-energy eg orbitals. CFSE values for octahedral
between the negative charge on the ligands and the electrons complexes are collected in Table 1.
in the metals d orbitals. Some of the most important inorganic chemistry textbooks
If the field created by the ligands were spherically sym- (13) contain a mistake. They include, incorrectly, the pairing
metrical, the d orbitals would remain degenerate, as they are energy in expressions of the crystal field stabilization energy
in an isolated, gaseous metal ion. Nevertheless, if six ligands of octahedral d 6 (and d7, d 8, d9, and d10) complexes. For
are at the corners of a regular octahedron, the five d orbit- example, the CFSE for high-spin d6 complexes is considered
als are no longer degenerate, but they split into two sets of to be 0.4o + P (13). Bearing in mind that for high-spin
orbitals, the t 2g orbitals (dxz , dyz , and d xy) and the eg orbitals complexes P > o, the above expression would lead to the
(dx2- y2 and dz2). The eg orbitals are exactly directed toward unrealistic result that CFSE is positive (i.e., the system would
the ligands and they have, therefore, a higher energy than be less stable for an octahedral field than for a spherical field).
the t 2g orbitals, which are oriented between adjacent ligands. The (wrong) inclusion of the pairing energy in the expres-
The energy difference between the two sets of orbitals is called sion CFSE = 0.4o + P is due to the fact that two electrons
o (or 10Dq), and the energies of the t2g and eg levels are, are paired in the same orbital for high-spin d6 complexes (see
respectively, 0.4o below and 0.6o above the energy of the Fig. 1). However, these electrons would also be paired in the
unsplit d orbitals. spherical ion. CFSE is the energy difference between the d

Table 1. Crystal Field Stabilization Energies (CFSE) for


Octahedral Complexes
dn Spin State Configuration CFSE
d 1
t2g1
0.4 o
d2 t2g1+1 0.8 o o -1.6 o + P
d4 low spin
d 3
t2g1+1+1
1.2 o
d4 high t2g1+1+1 eg1 0.6 o
low t2g2+1+1 1.6 o + P
d5 high t2g1+1+1 eg1+1 0
low t2g2+2+1 2.0 o + 2 P
d6 high t2g2+1+1 eg1+1 0.4 o
o -0.4 o
low t2g2+2+2 2.4 o + 2 P d6 high spin

d7 high t2g2+2+1 eg1+1 0.8 o


low t2g2+2+2 eg1 1.8 o + P
d8 t2g2+2+2 eg1+1 1.2 o Spherical field Octahedral field CFSE
d 9
t2g2+2+2
eg2+1
0.6 o
Figure 1. Crystal field splitting and CFSE for octahedral low-spin
d10 t2g2+2+2 eg2+2 0 d4 and high-spin d 6 complexes.

134 Journal of Chemical Education Vol. 76 No. 1 January 1999 JChemEd.chem.wisc.edu


Information Textbooks Media Resources

electrons in the spherical ion and the d electrons in the crystal Literature Cited
field (Fig. 1). Thus, although the pairing energy must be
1. Sharpe, A. G. Inorganic Chemistry, 3rd ed.; Longman: Essex,
included in the CFSE expression for low-spin d4 complexes,
U.K., 1992; p 469.
if electrons were paired in the spherical ion as in the high- 2. Huheey, J. E.; Keiter, E. A.; Keiter, R. L. Inorganic Chemistry,
spin d6 example (Fig. 1), there would be no additional pairing 4th ed.; Harper Collins: New York, 1993; p 400.
energy introduced by the octahedral field. Therefore, the 3. Cotton, F. A. ; Wilkinson, G.; Gaus, P. L. Basic Inorganic Chem-
CFSE for high-spin d6 complexes is 0.4o , as indicated in istry, 3rd ed.; Wiley: New York, 1995; p 515.
Table 1 and in the textbooks by Butler and Harrod (4) and 4. Butler, I. S.; Harrod, J. F. Inorganic Chemistry; Benjamin-
Rodgers (5). Cummings: Redwood City, CA, 1989; p 395.
It is interesting to note that the excellent textbooks by 5. Rodgers, G. E. Introduction to Coordination, Solid State, and De-
Huheey contained this kind of mistake in the first two scriptive Inorganic Chemistry; McGraw-Hill: New York, 1994; p
69.
editions (6, 7), and in the latest one (2), but not in the third
6. Huheey, J. E. Inorganic Chemistry; Harper and Row: New York,
edition (8). The expressions in Table 1 clearly show that for 1972; p 300.
d4, d5, d6, and d7 metal complexes, the most stable configu- 7. Huheey, J. E. Inorganic Chemistry, 2nd ed.; Harper and Row: New
rations are high spin if P > o, and low spin if o > P. This is York, 1978; p 353.
not so clear if the average pairing energy is not included in 8. Huheey, J. E. Inorganic Chemistry, 3rd ed.; Harper and Row: New
the CFSE expressions. York, 1983; p 374.

*Email: chmigorn@nus.edu.sg.

JChemEd.chem.wisc.edu Vol. 76 No. 1 January 1999 Journal of Chemical Education 135

You might also like