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

The vibrational and electronic structure of the bis(mu-nitrido) bridged complex [V(N{N"}2)(mu-N)]2 (1) (where [N{N"}2](2-)=[(Me3Si)N{CH(2)CH(2)N(SiMe3)}2](2-)) is analyzed. Assignment of the five modes of the V(2)(mu-N)2 core is based on (15)N 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 V(2)(mu-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 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.     

Penta-arylcyclopentadienyl complexes

This review covers the coordination and general chemistry of the 1,2,3,4,5-penta-arylcyclopentadiene system, as anion, C₅Ar₅^?, radical, C₅Ar₅, and cation, C₅Ar₅⁺, as well as the neutral diene, C₅Ar₅H, and its derivatives. The structural rigidity and steric saturation offered by the penta-arylcyclopentadienyl ligand give rise to definite structural and geometric properties in its complexes that distinguish its chemistry from that of the parent cyclopentadiene.