<i>N</i>‐Arylation and <i>N,N</i>‐Dibenzylation of Coordinated N₂ with Organic Halides; Differences in the Reactivity of <i>trans</i>‐[Mo(N₂)₂(Me₈[16]aneS₄)] and Its Phosphane Analogues

Abstract

The N2 ligand in the title complex (M8[16]anS4 = 3,3,7,7,11,11,15,15-octamethyl-1,5,9,13-tetrathiacyclohexadecane) displays unprecedented reactivity. It reacts with aryl halides and benzyl bromide in toluene at room temperature without irradiation to give MoII aryldiazenido and dibenzylhydrazido complexes, respectively. Its reaction with methanol and acetone affords NH3 and Me2CNNCMe2, respectively. Phosphane analogues of the title complex do not undergo such reactions. The structure of trans [MoI(N2-p-C6H4CO2Me)(Me8[16]anS4)], the diazenido complex, is shown on the right.