Electronic structures of tetragonal nitrido and nitrosyl metal complexes

Abstract

The standard oxidation states of central metal atoms in C_(4v) nitrido ([M(N)(L)₅]^z) complexes are four units higher than those in corresponding nitrosyls ([M(NO)(L)₅]^z) (L=CN: z = 3−, M = Mn, Tc, Re; z = 2−, M = Fe, Ru, Os; L = NH₃: z = 2+, M = Mn, Tc, Re; z = 3+, M = Fe, Ru, Os). Recent work has suggested that [Mn(NO)(CN)₅]³⁻ behaves electronically much closer to Mn(V)[b₂(xy)]², the ground state of [Mn(N)(CN)₅]³⁻, than to Mn(I)[b₂(xy)]²[e(xz,yz)]⁴. We have employed density functional theory and time-dependent density functional theory to calculate the properties of the ground states and lowest-lying excitations of [M(N)(L)₅]^z and [M(NO)(L)₅]^z . Our results show that [M(N)(L)₅]^z and [M(NO)(L)₅]^z complexes with the same z value have strikingly similar electronic structures.

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