Synthesis, Characterization, DFT Calculations, and Reactivity Study of a Nitrido-Bridged Dimeric Vanadium(IV) Complex

Two vanadium(III) complexes, CztBu(PyriPr)2VCl2 (1) and CztBu(PyriPr)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, [{CztBu(PyriPr)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.