Functionalization of N 2 to NH 3 via direct N ≡ N bond cleavage using M(III)(NMe 2 ) 3 (M=W/Mo): A theoretical study

Abstract

Atmospheric N2 can be cleaved directly to yield metal-nitride (before proceeding to the functionalization of N α of coordinated N2) and subsequently functionalized to ammonia using M(III)(NMe2)3 (M = W/Mo) as a catalyst, and suitable proton and electron sources. The calculated energies of thermodynamic and kinetic states of the various intermediates and transition states in the reaction coordinate to yield ammonia confirmed the viability of the proposed reaction pathway. Rationale of different pathways have been examined and discussed in detail. Changes in the structural features of the catalyst and some important intermediates and transition states have also been examined. N2 can be cleaved directly to form nitride complex and subsequently can be converted to ammonia in the presence of protons and electrons using M(III)(NMe2)3 (M = Mo/W) in a homogeneous solution under normal experimental conditions. The proposed pathway seems to be feasible based on the calculated thermodynamic and kinetic barriers.