Heterolytic N H bond activation of ammonia by dinuclear [{M(μ-OMe)}2] complexes (M = Sc – V and Mn – Ni): A theoretical investigation

In this present work, a computational study using B3LYP functional and 6-31+G(d,p) basis set has been performed to explore the detailed mechanism of the reaction between the complex [{M(μ-OMe)}2] and ammonia molecule leading to the formation of [{M(μ-NH2)}2] and methanol. The reaction involves the hydrogen transfer from NH3 molecule through the heterolytic NH bond cleavage. A number of 3d transition metals have been considered for this purpose. The preferential nucleophilic attack by NH3 has been justified by the calculated nucleophilicity indices, condensed to atom fukui parameter and local softness parameter. However, the subsequent heterolytic NH bond cleavage has been supported by using the NPA calculated atomic charges. The outcome of the present theoretical study of the investigated model complexes encompassing various 3d transition metals may be exploited in the industry to develop catalysts for NH bond activation process in synthesizing different inorganic and organic amine based compounds.