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Reactions of a platinum(II) agostic complex : decyclometalation, dicyclometalation, and solvent-switchable formation of a rollover complex

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Crosby, Sarah H., Clarkson, Guy J. and Rourke, Jonathan (2011) Reactions of a platinum(II) agostic complex : decyclometalation, dicyclometalation, and solvent-switchable formation of a rollover complex. Organometallics, Vol.30 (No.13). pp. 3603-3609. doi:10.1021/om200293e ISSN 0276-7333.

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Official URL: http://dx.doi.org/10.1021/om200293e

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Abstract

Good donor ligands react with an sp(2) cyclometalated complex of platinum containing an agostic interaction, initially causing displacement of the agostic interaction and decyclometalation. Eventually, these complexes rearrange to give sterically less congested complexes containing an sp(3) cydometalated group. The same end products are observed even with poor donor ligands that do not displace the agostic interaction, and this, together with other results, suggests to us that the route to the end products goes via a different agostic species. These sp(3) cyclometalated complexes can be made to dicyclometalate via the simple expedient of adding water/base. Finally, dissolution of the agostic complex in DMSO results in a reversible "rollover" reaction, giving a C(Lambda)C chelated ligand.

Item Type: Journal Article
Subjects: Q Science > QD Chemistry
Divisions: Faculty of Science, Engineering and Medicine > Science > Chemistry
Library of Congress Subject Headings (LCSH): Organometallic chemistry, Metal complexes, Dimethyl sulfoxide, Activation (Chemistry)
Journal or Publication Title: Organometallics
Publisher: American Chemical Society
ISSN: 0276-7333
Official Date: 11 July 2011
Dates:
DateEvent
11 July 2011Published
Volume: Vol.30
Number: No.13
Page Range: pp. 3603-3609
DOI: 10.1021/om200293e
Status: Peer Reviewed
Publication Status: Published
Access rights to Published version: Restricted or Subscription Access
Funder: University of Warwick, European Regional Development Fund (ERDF)

Data sourced from Thomson Reuters' Web of Knowledge

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