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

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 N_pyridineN_imineN_pyrrolide ligand (L²)⁻, a series of divalent Ni^IIX(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–N_pyrrolide) 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.