Reactions of nickel boranyl compounds with pnictogen–carbon triple bonds

The catalytic conversion of unsaturated small molecules such as nitriles into reduced products is of interest for the production of fine chemicals. In this vein, metal-ligand cooperativity has been leveraged to promote such reactivity, often conferring stability to bound substrate - a balancing act that may offer activation at the cost of turnover efficiency. This report describes the reactivity of a [(diphosphine)Ni] compound with pnictogen carbon triple bonds (R-C[triple bond, length as m-dash]E; E = N, P), where the diphosphine contains two pendant borane groups. For E = N, cooperative nitrile coordination is observed to afford {Ni}2 complexes displaying B-N interactions, whereas for E = P, B-P interactions are absent. This work additionally outlines a structure-activity relationship that uses nitrile dihydroboration as a model reaction to unveil the effect of SCS stabilization, employing [(diphosphine)Ni] where the diphosphine contains 0, 1, or 2 pendant Lewis acid groups.