Dinitrogen Cleavage by a Three-Coordinate Molybdenum(III) Complex

Abstract

Cleavage of the relatively inert dinitrogen (N(2)) molecule, with its extremely strong N identical withN triple bond, has represented a major challenge to the development of N(2) chemistry. This report describes the reductive cleavage of N(2) to two nitrido (N(3-)) ligands in its reaction with Mo(NRAr)(3), where R is C(CD(3))(2)CH(3) and Ar is 3,5-C(6)H(3)(CH(3))(2'), a synthetic three-coordinate molybdenum(III) complex of known structure. The formation of an intermediate complex was observed spectroscopically, and its conversion (with N identical withN bond cleavage) to the nitrido molybdenum(VI) product N identical withMo(NRAr)(3) followed first-order kinetics at 30 degrees C. It is proposed that the cleavage reaction proceeds by way of an intermediate complex in which N(2) bridges two molybdenum centers.

Highlights in the Renaissance of Amidometal Chemistry

“…[229] Ten years before the existence of the MP species had already been discussed. [230] The tendency of compound 60 to react with N 2 [212] or N 2 O [211] by NÀN bond cleavage to form the nitrido complex and the affinity of the [(TMSN 3 N)W] fragment for the spontaneous formation of metal ± carbon triple bonds [223,219] suggest that both systems are set up for the stabilization of a terminal P 1 ligand.…”

Inner-sphere two-electron reduction leads to cleavage and functionalization of coordinated dinitrogen

“…Stoichiometric cleavage of the strong N-N bond has been observed for groups 5 and 6 metal complexes (20)(21)(22)(23)(24)(25), certain dinuclear zirconium dinitrogen complexes have been found to react with H 2 to generate N-H bonds (26)(27)(28), and terminal alkynes have been found to react with coordinated N 2 in a side-on bound dizirconium complex to generate a N-C bond (29). These processes have expanded the toolbox of fundamental reactions for coordinated dinitrogen.…”

Activation of Molecular Nitrogen: Coordination, Cleavage and Functionalization of N2 Mediated By Metal Complexes

“…3 . [69,70] Since this discovery, numerous other dinitrogen cleavage reactions have been reported. An isoelectronic vanadium system with a diamidoamine ligand set [71] and a niobium calixarene reduced with sodium [72,73] (Figure 12).…”