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Oxidation of an o -tolyl phosphine complex of platinum: C-H activation and transcyclometallation

Shaw, Paul A., Clarkson, Guy J. and Rourke, Jonathan P. 2017. Oxidation of an o -tolyl phosphine complex of platinum: C-H activation and transcyclometallation. Journal of Organometallic Chemistry 851 , pp. 115-121. 10.1016/j.jorganchem.2017.09.026

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Abstract

The oxidation of the tri(o-tolyl)phospine complex of the doubly cyloplatinated 2,6-di(4-fluorophenyl)pyridine ligand with the electrophilic oxidant iodobenzenedichloride was studied. Three products were formed in the ratio 15:15:70, and all were identified. The simple cis-dichloro platinum(IV) complex 2 (15%) remained in solution and could be purified and fully characterised. The triply cyclometallated 3 (15%), formed via the activation of a methyl group on a tolyl ring, precipitated from the reaction mixture and could not be redissolved or characterised further. Transcyclometallated 4 (70%), where one of the original cyclometallated aryl rings has exchanged for a cyclometallated phosphine ring, crystallised from the reaction mixture and was characterised crystallographically. Redissolution of 4 gave a new agostic species with the phosphine moving to a less sterically demanding position.

Item Type: Article
Date Type: Publication
Status: Published
Schools: Chemistry
Publisher: Elsevier
ISSN: 0022-328X
Date of First Compliant Deposit: 17 January 2019
Date of Acceptance: 16 September 2017
Last Modified: 30 Jun 2019 19:56
URI: http://orca-mwe.cf.ac.uk/id/eprint/118478

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