Dinitrogen‐Molybdenum Complex Induces Dinitrogen Cleavage by One‐Electron Oxidation

Abstract

Abstract Reported here is the N 2 cleavage of a one‐electron oxidation reaction using trans ‐[Mo(depe) 2 (N 2 ) 2 ] ( 1 ) (depe=Et 2 PCH 2 CH 2 PEt 2 ), which is a classical molybdenum(0)‐dinitrogen complex supported by two bidentate phosphine ligands. The molybdenum(IV) terminal nitride complex [Mo(depe) 2 N][BArf 4 ] ( 2 ) (BArf 4 =B(3,5‐(CF 3 ) 2 C 6 H 3 ) 4 ) is synthesized by the one‐electron oxidation of 1 upon addition of a mild oxidant, [Cp 2 Fe][BArf 4 ] (Cp=C 5 H 5 ), and proceeds by N 2 cleavage from a Mo II ‐N=N‐Mo II structure. In addition, the electrochemical oxidation reaction for 1 also cleaved the N 2 ligand to give 2 . The dimeric Mo complex with a bridging N 2 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 I species is converted into 2 via the dimeric structure involving a zigzag transition state.