Insights into Activation of Cobalt Pre-Catalysts for C(sp²)−H Functionalization

The activation of readily prepared, air-stable cobalt(II) bis(carboxylate) pre-catalysts for the functionalization of C(sp²)−H bonds has been systematically studied. With the pyridine bis(phosphine) chelate, ^iPrPNP, treatment of 1-(O₂C^tBu)₂ with either B₂Pin₂ or HBPin generated cobalt boryl products. With the former, reduction to (^iPrPNP)Co^IBPin was observed while with the latter, oxidation to the cobalt(III) dihydride boryl, trans-(^iPrPNP)Co(H)₂BPin occurred. The catalytically inactive cobalt complex, Co[PinB(O₂C^tBu)₂]₂, accompanied formation of the cobalt-boryl products in both cases. These results demonstrate that the pre-catalyst activation from cobalt(II) bis(carboxylates), although effective and utilizes an air-stable precursor, is less efficient than activation of cobalt(I) alkyl or cobalt(III) dihydride boryl complexes, which are quantitatively converted to the catalytically relevant cobalt(I) boryl. Related cobalt(III) dihydride silyl and cobalt(I) silyl complexes were also synthesized from treatment of trans-(^iPrPNP)Co(H)₂BPin and (^iPrPNP)CoPh with HSi(OEt)₃, respectively. No catalytic silylation of arenes was observed with either complex likely due to the kinetic preference for reversible C−H reductive elimination rather than product- forming C−Si bond formation from cobalt(III). Syntheses of the cobalt(II) bis(carboxylate) and cobalt(I) alkyl of ^iPrPONOP, a pincer where the methylene spacers have been replaced by oxygen atoms, were unsuccessful due to deleterious P−O bond cleavage of the pincer. Despite their structural similarity, the rich catalytic chemistry of ^iPrPNP was not translated to ^iPrPONOP due to the inability to access stable cobalt precursors as a result of ligand decomposition via P−O bond cleavage.