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Trapping five-coordinate platinum(IV) intermediates

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Shaw, Paul Anthony, Phillips, Jessica M., Clarkson, Guy J. and Rourke, Jonathan (2016) Trapping five-coordinate platinum(IV) intermediates. Dalton Transactions, 45 (28). 11397-11406 . doi:10.1039/c6dt02088g

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Official URL: http://dx.doi.org/10.1039/C6DT02088G

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Abstract

The oxidation of three different complexes of the doubly cyloplatinated 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 (2t), which subsequently isomerises to the cis isomer (2c). 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 trans-cyclometallation reaction to give a complex with a singly cyclometallated pyridine and a cyclometallated phosphine, which was characterised crystallographically, (6c(c)).

Item Type: Journal Article
Subjects: Q Science > QD Chemistry
Divisions: Faculty of Science > Chemistry
Library of Congress Subject Headings (LCSH): Pyridine -- Oxidation, Platinum
Journal or Publication Title: Dalton Transactions
Publisher: Royal Society of Chemistry
ISSN: 1477-9226
Official Date: 28 July 2016
Dates:
DateEvent
28 July 2016Published
17 June 2016Available
17 June 2016Accepted
24 May 2016Submitted
Date of first compliant deposit: 22 June 2016
Volume: 45
Number: 28
Page Range: 11397-11406
DOI: 10.1039/c6dt02088g
Status: Peer Reviewed
Publication Status: Published
Access rights to Published version: Restricted or Subscription Access
Funder: Engineering and Physical Sciences Research Council (EPSRC), Advantage West Midlands (AWM), European Regional Development Fund (ERDF)

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