Nickel complexes of a PC(carbene)P pincer ligand framework are described. Dehydrobromination of the precursor (PC(sp)(3)P)NiBr in the presence of a donor (PPh3 or NC(t)Bu) leads to the title complexes, which feature a rare nickel-carbene linkage as the pincer ligand anchor point. This strongly donating, nucleophilic carbene center engages in a variety of E-H bond activations (E = H, C, N, O), some of which are reversible. This represents a new mode of bond activation by ligand cooperativity in nickel pincer complexes.

Hydrosilylation of carbonyls catalyzed by 2 goes via intermediate formation of cationic silane sigma-complexes 4 which undergo nucleophilic abstraction of the silylium cation studied by DFT calculations.

Reactions of a new borohydride complex 2 with hydrosilanes afford half-sandwich dihydride silyl complexes 3a-f. According to X-ray and DFT evidence complexes 3 have unprecedented double H...Si...H interligand interactions.