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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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WRAP-oxidation-tolyl-phosphine-platinum-Rouke-2017.pdf - Accepted Version - Requires a PDF viewer. Available under License Creative Commons Attribution Non-commercial No Derivatives 4.0. Download (887Kb) | Preview |
Official URL: http://dx.doi.org/10.1016/j.jorganchem.2017.09.026
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 | ||||||
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| 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: |
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| Date of first compliant deposit: | 28 September 2017 | ||||||
| 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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