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

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

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Official URL: http://dx.doi.org/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: Journal Article
Subjects: Q Science > QD Chemistry
Divisions: Faculty of Science > Chemistry
Library of Congress Subject Headings (LCSH): Platinum -- Oxidation, Phosphine
Journal or Publication Title: Journal of Organometallic Chemistry
Publisher: Elsevier S.A.
ISSN: 0022-328X
Official Date: 15 November 2017
Dates:
DateEvent
15 November 2017Published
19 September 2017Available
Volume: 851
Page Range: pp. 115-121
DOI: 10.1016/j.jorganchem.2017.09.026
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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