Dynamics of intersystem crossing processes in solution for six-coordinate d/sup 5/, d/sup 6/, and d/sup 7/ spin-equilibrium metal complexes of iron(III), iron(II), and cobalt(II)
Intersystem crossing rates for 14 (low-spin) reversible (high-spin) spin-equilibrium metal complexes of six-coordinate iron-(II) (/sup 1/A reversible /sup 5/T; ..delta..S = 2), iron(III) (/sup 2/T reversible /sup 6/A; ..delta..S = 2), and cobalt(II) (/sup 2/E reversible /sup 4/T; ..delta..S = 1) have been investigated in solution by Raman laser temperature-jump kinetics. Measurable first-order rate constants for the forward (k/sub 1/) and reverse (k-/sub 1/) processes range from 4 x 10/sup 5/ to 2 x 10/sup 7/ s/sup -1/, with four of the complexes having rate constants too large to measure (approximately greater than 2 x 10/sup 7/ s/sup -1/) by the technique. The results are interpreted in terms of a model in which the spin multiplicity change is treated as an internal electron-transfer reaction.
- Research Organization:
- Rice Univ., Houston, TX
- OSTI ID:
- 5200473
- Journal Information:
- J. Am. Chem. Soc.; (United States), Vol. 100:4
- Country of Publication:
- United States
- Language:
- English
Similar Records
Solution-state spin-equilibrium properties of the tris(2-(2-pyridyl)imidazole)iron(II) and Tris(2-(2-pyridyl)benzimidazole)iron(II) cations
Direct measurement of spin-state lifetimes in solution for some iron(II) spin equilibrium complexes derived from hexadentate ligands. [Methanol and aqueous solutions]