Electronic structures of tetragonal nitrido and nitrosyl metal complexes
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- Hummel, P., Winkler, J.R. & Gray, H.B. Theor Chem Account (2008) 119: 35. doi:10.1007/s00214-006-0236-8
The standard oxidation states of central metal atoms in C4v 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.