Tanabe Sugano
Tanabe Sugano
Tanabe Sugano
• The d-electron-d-electron repulsions present in dX metal complexes with x > 1 make the
relationship between the d-orbital splitting parameter D and absorption frequencies complex.
• The following equations relate D, the electron repulsion parameter B’ and transition
frequencies n1, n2, n3 (n1 < n2 < n3) for d3 and d8 octahedral complexes:
Energy d3, d8 O d2, d7 Oh
h
d2, d7 Td d3, d8 Td A2
n1 = D T1(P)
n2 = 7.5B’ + 1.5D - 0.5 [225 B’2+D2-18B’D]1/2 T1g(P)
T1(F)
n3 = 7.5B’ + 1.5D + 0.5 [225 B’2+D2-18B’D]1/2 T2g
T2
T1g(F)
A2
D 0 D
• For example, for d3 chromium(III) complex CrF63- the absorptions are at 14900, 22700 and
34400 cm-1.
• From the formulas above D = 14900 cm-1, n2 + n3 = 15B’ + 3D = 57100
• Therefore, 15B’ = 12400 and B’ ≈ 827 cm-1.
2) Tanabe-Sugano diagrams. d2 octahedral complexes
IN
2
• Tanabe-Sugano diagrams have been calculated for d
the cases of all ligand field strengths for all
octahedral dn-metal complex configurations.
• The diagrams allow for estimation of a complete set
of parameters included in the calculations: i) the
(apparent) electron repulsion parameter B’, ii) D, iii)
transition frequencies. 52
4
P
4 4
4 T A2
G 4 1
4
E 4
E (t2)4(e)1
4
T2 T 2 3
4 4 2 (t2) (e)
T1 T1
6
S 6 5
A1 2(t 2 )
T2
(t2)1(e)4
octahedral and tetrahedral d5
4) Weak ligand fields, all dn configurations: the number and
intensity of bands
• The number of the spin-allowed electronic transitions for all dn metal configurations for
the case of weak ligand fields is given in table below.
• The intensity of absorption bands can be evaluated on the basis of the selection rules.
The symmetry forbidden d-d transitions for d1-d4, d6-d9 complexes below have e in the
range of 1 – 103 L/(mol cm). Both symmetry and spin forbidden transitions for d5
complexes have e of 0.001 – 1 L/(mol cm).
4A (G)
1g
4E (G)
g
4T (G)
1g
4T (G)
2g