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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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WRAP_9470222-ch-210616-r2_manuscript.pdf - Accepted Version - Requires a PDF viewer. Download (1165Kb) | Preview |
Official URL: http://dx.doi.org/10.1039/C6DT02088G
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 | ||||||||||
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| 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: |
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| 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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