Synthesis, characterization, DFT calculations, and reactivity study of a nitrido-bridged dimeric vanadium(iv) complex

Abstract

Two vanadium(III) complexes, Cz^tBu(Pyr^iPr)₂VCl₂ (1) and Cz^tBu(Pyr^iPr)₂V(N₃)₂ (2), were synthesized and characterized. Chemical reduction of both 1 and 2 gives the thermally stable nitrido-bridged vanadium(IV) dimer complex, [{Cz^tBu(Pyr^iPr)₂}V]₂(μ-N)₂ (3), which is a rare example of a dimeric vanadium(IV) complex bridged by two nitrido ligands. The nitride ligands of 3 are unreactive due to the well-protected environment provided by the pincer ligand and its substituents, as is supported by its X-ray crystal structure and further described by DFT calculations.