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This chapter focuses on vanadium nitrogenase and vanadium complexes showing catalytic reactivity relevant to nitrogenase. The structural and catalytic features of the protein are described. Examples of synthetic vanadium complexes serving as catalysts for (1) dinitrogen reduction to ammonia, (2) silylation of N2 into silylamine and (3) reduction and disproportionation of N2H4 into NH3 are documented.

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