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)2 diamond core

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{CH 2CH2N(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.