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Selective C-C coupling at a Pt(IV) centre: 100% preference for sp2-sp3 over sp3-sp3

Shaw, Paul A. and Rourke, Jonathan P. 2017. Selective C-C coupling at a Pt(IV) centre: 100% preference for sp2-sp3 over sp3-sp3. Dalton Transactions 46 (14) , pp. 4768-4776. 10.1039/C7DT00328E

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Abstract

The oxidative addition of three different organic halides RX to the non-symmetric platinum(II) mer coordinated dicyclometallated C^N^C complex 1 yielded short-lived six-coordinate platinum(IV) complexes 2(R) (R = Me, allyl, Bn), with the incoming groups trans across the platinum centre. A spontaneous reductive coupling reaction then occurred with, in each case, a completely chemoselective sp2–sp3 coupling, and exclusively gave R-3, with the newly introduced R group bonded to the previously cyclometallated aryl ring. Following a recyclometallation reaction, the oxidative addition/reductive elimination cycle was repeated and gave the same selectivity. A one-pot route to doubly alkylating the aryl ring was developed. The observed selectivity might have been predicted on the normal basis of a steric barrier associated with non-flat sp3 hybridised groups, but we suggest that it arises from the stereochemistry at the metal, and the orientation of the ligands.

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: 20 March 2017
Last Modified: 18 Oct 2019 06:33
URI: http://orca-mwe.cf.ac.uk/id/eprint/118508

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