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Issue 27, 2019
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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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Supplementary files

Article information


Submitted
01 Jun 2019
Accepted
05 Jun 2019
First published
07 Jun 2019

Dalton Trans., 2019,48, 9920-9924
Article type
Communication

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, 48, 9920
DOI: 10.1039/C9DT02313E

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