Factors That Affect the Magnitude of Δo
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20-6-2019
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Factors That Affect the Magnitude of Δo
The magnitude of Δo dictates whether a complex with four, five, six, or seven d electrons is high spin or low spin, which affects its magnetic properties, structure, and reactivity. Large values of Δo (i.e., Δo > P) yield a low-spin complex, whereas small values of Δo (i.e., Δo < P) produce a high-spin complex. As we noted, the magnitude of Δo depends on three factors: the charge on the metal ion, the principal quantum number of the metal (and thus its location in the periodic table), and the nature of the ligand. Values of Δo for some representative transition-metal complexes are given in Table 1.1.
Table 1.1 : Crystal Field Splitting Energies for Some Octahedral (Δo)* and Tetrahedral (Δt) Transition-Metal Complexes
| Octahedral Complexes |
Δo (cm−1) |
Octahedral Complexes |
Δo (cm−1) |
Tetrahedral Complexes |
Δt (cm−1) |
| *Energies obtained by spectroscopic measurements are often given in units of wave numbers (cm−1); the wave number is the reciprocal of the wavelength of the corresponding electromagnetic radiation expressed in centimeters: 1 cm−1 = 11.96 J/mol. |
| [Ti(H2O)6]3+ |
20,300 |
[Fe(CN)6]4− |
32,800 |
VCl4 |
9010 |
| [V(H2O)6]2+ |
12,600 |
[Fe(CN)6]3− |
35,000 |
[CoCl4]2− |
3300 |
| [V(H2O)6]3+ |
18,900 |
[CoF6]3− |
13,000 |
[CoBr4]2− |
2900 |
| [CrCl6]3− |
13,000 |
[Co(H2O)6]2+ |
9300 |
[CoI4]2− |
2700 |
| [Cr(H2O)6]2+ |
13,900 |
[Co(H2O)6]3+ |
27,000 |
|
|
| [Cr(H2O)6]3+ |
17,400 |
[Co(NH3)6]3+ |
22,900 |
|
|
| [Cr(NH3)6]3+ |
21,500 |
[Co(CN)6]3− |
34,800 |
|
|
| [Cr(CN)6]3− |
26,600 |
[Ni(H2O)6]2+ |
8500 |
|
|
| Cr(CO)6 |
34,150 |
[Ni(NH3)6]2+ |
10,800 |
|
|
| [MnCl6]4− |
7500 |
[RhCl6]3− |
20,400 |
|
|
| [Mn(H2O)6]2+ |
8500 |
[Rh(H2O)6]3+ |
27,000 |
|
|
| [MnCl6]3− |
20,000 |
[Rh(NH3)6]3+ |
34,000 |
|
|
| [Mn(H2O)6]3+ |
21,000 |
[Rh(CN)6]3− |
45,500 |
|
|
| [Fe(H2O)6]2+ |
10,400 |
[IrCl6]3− |
25,000 |
|
|
| [Fe(H2O)6]3+ |
14,300 |
[Ir(NH3)6]3+ |
41,000 |
|
|
Source of data: Duward F. Shriver, Peter W. Atkins, and Cooper H. Langford, Inorganic Chemistry, 2nd ed. (New York: W. H. Freeman and Company, 1994).
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