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Trapping five-coordinate platinum(IV) intermediates

Shaw, Paul A., Phillips, Jessica M., Clarkson, Guy J. and Rourke, Jonathan P. ORCID: 2016. Trapping five-coordinate platinum(IV) intermediates. Dalton Transactions 45 (28) , pp. 11397-11406. 10.1039/C6DT02088G

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The oxidation of three different complexes of the doubly cycloplatinated 2,6-di(4-fluorophenyl)pyridine ligand (namely DMSO, PPh3 and PPr3 derivatives, 1a, 1b and 1c, respectively) with the electrophilic oxidant iodobenzenedichloride was studied. In each case oxidation can yield a simple trans-dichloro platinum(IV) complex (2(t)), which subsequently isomerises to the cis isomer (2(c)). However, by changing the solvent, or performing the reaction in the presence of an additional ligating species, a five-coordinate intermediate can be trapped out and isolated. Thus, cationic species with additional DMSO or pyridine coordinated could be collected for the DMSO and PPh3 derivatives. The PPr3 derivative traps out the reactive five-coordinate species with an agostic interaction that subsequently induces a transcyclometallation reaction to give a complex with a singly cyclometallated pyridine and a cyclometallated phosphine, which was characterised crystallographically,

Item Type: Article
Date Type: Publication
Status: Published
Schools: Chemistry
Publisher: Royal Society of Chemistry
ISSN: 1477-9226
Date of First Compliant Deposit: 17 January 2019
Date of Acceptance: 17 June 2016
Last Modified: 26 Dec 2022 10:54

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