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

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Abstract

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.

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

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Publication details

The article was received on 01 Jun 2019, accepted on 05 Jun 2019 and first published on 07 Jun 2019


Article type: Communication
DOI: 10.1039/C9DT02313E
Dalton Trans., 2019, Advance Article

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

    S. Sung, H. Tinnermann, T. Krämer and R. D. Young, Dalton Trans., 2019, Advance Article , DOI: 10.1039/C9DT02313E

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