Spectroscopic Evidence of a Reduced Alkenylnickel Intermediate in Catalytic Markovnikov-Selective Alkyne Hydroboration

Abstract

Nickel-catalyzed hydrofunctionalization reactions, including the hydroboration of alkynes, have been generally proposed to proceed via classical two-electron pathways or, alternatively, through a NiIH-based insertion mechanism. Despite efforts to discern these pathways, explicit spectroscopic observation of NiIH species and relevant mechanistic information on LNiI(alkenyl) species remain lacking. Herein, we provide experimental evidence of formal NiI intermediates, suggestive of a NiIH-based insertion mechanism for alkyne hydroboration. The formation of a NiI catalyst precursor, LnNiI(dpm) (dpm = dipivaloylmethanate anion) and an LnNi(alkenyl) intermediate was confirmed by EPR spectroscopy and HRMS analysis. Their involvement in the catalytic reaction was demonstrated by stoichiometric and catalytic reactivity studies. The origin of the counterintuitive Markovnikov selectivity in the formation of the α-alkenylboronate product was probed by systematic ligand electronic effect studies. Computational analyses rationalize the selectivity by a kinetic preference for formation of the α regioisomer of the LnNi(alkenyl) intermediate through noncovalent interactions.