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Long-lived five-coordinate platinum(IV) intermediates: regiospecific C-C coupling

Shaw, Paul A., Clarkson, Guy J. and Rourke, Jonathan P. ORCID: 2016. Long-lived five-coordinate platinum(IV) intermediates: regiospecific C-C coupling. Organometallics 35 (21) , pp. 3751-3762. 10.1021/acs.organomet.6b00697

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Three different phosphine derivatives of doubly cyclometalated diphenypyridine complexes of Pt(II), 1, were reacted with methyl iodide to give octahedral Pt(IV) complexes, 2, as two isomers. Treatment of either isomer of complexes 2 with AgBF4, to abstract iodide, gave long-lived five-coordinate complexes 3, which could be trapped as pyridine adducts. Complexes 3 underwent a C–C coupling reaction, at a rate that depended on phosphine size, to give a methyl group attached to the original diphenylpyridine. Recylometalation was then performed, and the cycle of reactions was repeated to give a diphenylpyridine doubly methylated on only one phenyl, with complete regiospecificity. NMR was used to demonstrate the geometry of all complexes in solution, with multiple X-ray crystal structures confirming these assignments.

Item Type: Article
Date Type: Publication
Status: Published
Schools: Chemistry
Publisher: American Chemical Society
ISSN: 0276-7333
Date of First Compliant Deposit: 17 January 2019
Date of Acceptance: 26 October 2016
Last Modified: 25 Dec 2022 05:05

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