Reactions of a platinum(II) agostic complex: decyclometalation, dcyclometalation, and solvent-switchable formation of a rollover complex

Crosby, Sarah H., Clarkson, Guy J. and Rourke, Jonathan P. ORCID: https://orcid.org/0000-0002-8961-1021 2011. Reactions of a platinum(II) agostic complex: decyclometalation, dcyclometalation, and solvent-switchable formation of a rollover complex. Organometallics 30 (13) , pp. 3603-3609. 10.1021/om200293e

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Abstract

Good donor ligands react with an sp2 cyclometalated complex of platinum containing an agostic interaction, initially causing displacement of the agostic interaction and decyclometalation. Eventually, these complexes rearrange to give sterically less congested complexes containing an sp3 cyclometalated group. The same end products are observed even with poor donor ligands that do not displace the agostic interaction, and this, together with other results, suggests to us that the route to the end products goes via a different agostic species. These sp3 cyclometalated complexes can be made to dicyclometalate via the simple expedient of adding water/base. Finally, dissolution of the agostic complex in DMSO results in a reversible “rollover” reaction, giving a C∧C chelated ligand.

Item Type:	Article
Date Type:	Publication
Status:	Published
Schools:	Chemistry
Publisher:	American Chemical Society
ISSN:	0276-7333
Last Modified:	03 Apr 2023 16:00
URI:	https://orca.cardiff.ac.uk/id/eprint/155167

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