Comparing B–H Bond Activation in Ni^IIX(NNN)-Catalyzed Nitrile Dihydroboration (X = Anionic N-, C-, O-, S-, or P-donor)

Abstract

One of the key steps in many metal complex-catalyzed hydroboration reactions is B–H bond activation, which results in metal hydride formation. Anionic ligands that include multiple lone pairs of electrons, in cooperation with a metal center, have notable potential in redox-neutral B–H bond activation through metal–ligand cooperation. Herein, using an easily prepared NpyridineNimineNpyrrolide ligand (L2)−, a series of divalent NiIIX(NNN) complexes were synthesized, with X = bromide (2), phenoxide (3), thiophenoxide (4), 2,5-dimethylpyrrolide (5), diphenylphosphide (6), and phenyl (7). The complexes were characterized using 1H and 13C NMR spectroscopy, mass spectrometry, and X-ray crystallography and employed as precatalysts for nitrile dihydroboration. Superior activity of the phenoxy derivative (3) [vs thiophenoxy (4) or phenyl (7)] suggests that B–H bond activation occurs at the Ni–X (vs ligand Ni–Npyrrolide) bond. Furthermore, stoichiometric treatment of 2–7 with a nitrile showed no reaction, whereas stoichiometric reactions of 2–7 with pinacolborane (HBpin) gave the same Ni–H complex for 2, 3, and 5. Considering that only 2, 3, and 5 successfully catalyzed nitrile dihydroboration, we suggest that the catalytic cycle involves a conventional inner sphere pathway initiated by substrate insertion into Ni–H.