Dinitrogen-Molybdenum Complex Induces Dinitrogen Cleavage by One-Electron Oxidation.

Reported here is the N cleavage of a one-electron oxidation reaction using trans-[Mo(depe) (N ) ] (1) (depe=Et PCH CH PEt ), which is a classical molybdenum(0)-dinitrogen complex supported by two bidentate phosphine ligands. The molybdenum(IV) terminal nitride complex [Mo(depe) N][BArf ] (2) (BArf =B(3,5-(CF ) C H ) ) is synthesized by the one-electron oxidation of 1 upon addition of a mild oxidant, [Cp Fe][BArf ] (Cp=C H ), and proceeds by N cleavage from a Mo -N=N-Mo structure. In addition, the electrochemical oxidation reaction for 1 also cleaved the N ligand to give 2. The dimeric Mo complex with a bridging N is detected by in situ resonance Raman and in situ UV-vis spectroscopies during the electrochemical oxidation reaction for 1. Density-functional theory (DFT) calculations reveal that the unstable monomeric oxidized Mo species is converted into 2 via the dimeric structure involving a zigzag transition state.