Covalency factors of first-row transition-metal fluoride complex ions from electron spin resonance measurements

Abstract

From an established MO treatment of six-co-ordinate fluoride octahedral metal complexes, covalency factors are defined in terms of metal and ligand orbital admixture coefficients and metal-to-ligand overlap integrals. These covalency factors are related to experimental g-values, the hyperfine splitting constant, and ¹⁹F superhyperfine splitting constants from e.s.r. measurements. These covalency factors and the electron spin density transfer coefficients (to fluorine) for antibonding π orbitals of the t_2g³ configuration were approximately ca. 0·1–0·2 and were, in general, exceeded by the corresponding covalency factors and coefficients for the t_2g³e_g² and t_2g⁶e_g² configuration's antibonding σ orbitals.