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


Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore 117543, Singapore. [Email]


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 PCcarbeneP(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 PCcarbeneP pincer complex (2), where bisphosphines were used as oxide sequestering agents.

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