Electronic structures of tetragonal nitrido and nitrosyl metal complexes |
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| Authors: | Patrick Hummel Jay R Winkler Harry B Gray |
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| Institution: | (1) California Institute of Technology, Mail Code 139-74, Pasadena, CA 91125, USA |
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| 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)b
2(xy)]2, the ground state of Mn(N)(CN)5]3−, than to Mn(I)b
2(xy)]2e(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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| Keywords: | Density functional theory Time dependent density functional theory Electronic structures Nitrido Nitric oxide |
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