Direct oxide transfer from an η²-keto ligand to generate a cobalt PC_carbeneP(O) pincer complex

We report the direct carbonyl cleavage in a κ³-P',(η²-C,O),P'' ligand by a monomeric cobalt centre through metal-ligand cooperativity. C-O cleavage leads to the formation of a PC_carbeneP(O) pincer ligand with a central alkylidene anchor. A DFT analysis, supported by kinetic studies, suggests that decoordination of a pincer phosphino arm to generate a kinetically accessible free phosphine may be critical in transfer of the oxide to a phosphorus position. Thus, oxide transfer to bisphosphino bidentate co-ligands was also found to be viable, allowing access to the previously reported PC_carbeneP pincer complex (2), where bisphosphines were used as oxide sequestering agents.