A Dinitrogen Divanadium Complex Supported by a Trisamidophosphine Ligand

Comprehensive Summary The reaction between tripodal trisamidophosphine ligand H 3 PN 3 Ar and V(Mes) 3 (THF) (Mes = mesityl) yields the vanadium(III) complex (PN 3 Ar )V ( 1 ) with an open site in the axial position, which could coordinate with THF, pyridine, and NH 3 to form the corresponding adducts ( 2 — 4 ). The vanadium(III) center is redox‐active, as demonstrated by cyclic voltammetry methods and chemical oxidation or reduction. Notably, a novel dinitrogen divanadium complex with a bridging N 2 ligand, {K(THF)} 2 {[PN 3 Ar ]V} 2 ( μ ‐N 2 ) ( 6 ), was synthesized via treatment of 1 with 1 equivalent of potassium naphthalenide in THF under a N 2 atmosphere. The electronic structures and binding properties of 6 are evaluated and discussed based on its DFT calculations. Additionally, these vanadium complexes ( 1 , 5 , 6 ) can serve as catalysts for the conversion of N 2 into N(SiMe 3 ) 3 in the presence of reductants and Me 3 SiCl.