Theoretical Chemistry Accounts

, Volume 119, Issue 1, pp 35–38

Electronic structures of tetragonal nitrido and nitrosyl metal complexes

Regular Article

DOI: 10.1007/s00214-006-0236-8

Cite this article as:
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 =  NH3z = 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.


Density functional theory Time dependent density functional theory Electronic structures Nitrido Nitric oxide 

Copyright information

© Springer-Verlag 2007

Authors and Affiliations

  • Patrick Hummel
    • 1
  • Jay R. Winkler
    • 1
  • Harry B. Gray
    • 1
  1. 1.California Institute of TechnologyPasadenaUSA

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