Preparation of a borane-appended Co(III) hydride: evidence for metal-ligand cooperativity in O-H bond activation.

Cobalt hydrides are known to mediate a number of important chemical transformations including proton (H+), hydride (H-), and hydrogen-atom (H˙) transfer. Central to the tunability of such frameworks is judicious ligand design, which offers the flexibility to alter fundamental properties relevant to reactivity. Herein, we report the preparation of one such cobalt(III) hydride: [Cp*CoIII(P2BCy4)(H)]BPh4 (Cp* = C5Me5-, P2BCy4 = 1,2-bis(di(3-dicyclohexylborane)propylphosphino)ethane) that is encircled by a boron-based Lewis-acidic secondary coordination sphere. The structure of this species is supported by synchrotron-radiation crystallography, evidencing a terminal Co(III) hydride with four sp2-hybridized boranes that invite Lewis base coordination. To this end, electrochemical reactivity studies performed using [Cp*CoIII(P2BCy4)Cl]+ or an "all-akyl" model, [Cp*CoIII(dnppe)Cl]+ (dnppe = 1,2-bis(di-n-propylphosphino)ethane) with benzoic or 4-pyridylbenzoic acid show divergent responses for protonation of electrochemically-generated Co(I) to give a Co(III) hydride. For [Cp*CoIII(P2BCy4)Cl]+, this process is complex, not only involving protonation, but also engagement of the pendant borane moieties in Lewis acid/base interactions. For protonation by benzoic acid, for example, borane-benzoate contacts are substantiated by variable temperature NMR spectroscopic measurements and theoretical calculations, pointing to a cooperative Co-H/B-O bond forming process. These data are discussed in the context of designing new molecular catalysts for ligand-assisted hydrogen evolution reactivity.