Vibrational and electronic structure of the dinuclear bis(µ-nitrido) vanadium(v) complex [V(N{N″}2)(µ-N)]2: spectroscopic properties of the M2(µ-N)2diamond core

Abstract

The vibrational and electronic structure of the bis-µ-nitrido bridged complex [V(N{N″}₂)(µ-N)]₂ (1) (where [N{N″}₂]²⁻ = [(Me₃Si)N{CH₂CH₂N(SiMe₃)}₂]²⁻) is analyzed. Assignment of the five modes of the V₂(µ-N)₂ core is based on ¹⁵N isotope shifts and a DFT calculation on the calculated structure I which is an exact reproduction of 1. The three Raman active modes of the planar V₂(µ-N)₂ core are found in the Raman spectrum whereas the two IR allowed vibrations are identified in the infrared spectrum. Furthermore, the electronic structure of 1 is described which complements earlier theoretical studies on the reaction pathway leading to 1 (V. M. E. Bates, G. K. B. Clentsmith, F. G. N. Cloke, J. C. Green, H. D. L. Jenkin, Chem. Commun., 2000, 927). Based on the MO scheme of I the UV-vis transitions of 1 are assigned.