Platinum(II) and platinum(IV) complexes stabilized by abnormal/mesoionic C4-bound dicarbenes

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Title: Platinum(II) and platinum(IV) complexes stabilized by abnormal/mesoionic C4-bound dicarbenes
Authors: Khlebnikov, Vsevolod
Heckenroth, Marion
Müller-Bunz, Helge
Albrecht, Martin
Permanent link: http://hdl.handle.net/10197/6832
Date: 28-Mar-2013
Abstract: Platinum(II) complexes comprising abnormal diimidazolylidene ligands were synthesized from cis-PtMe2(DMSO)(2) using microwave-assisted double C-H bond activation. NMR analysis revealed an unusual solvolysis process, induced by coordinating solvents such as DMSO and MeCN, which has not been observed in related normal dicarbene complexes. NMR and IR spectroscopy and crystallographic analysis of the mono-substituted DMSO complex indicate a sulfur-bonding of the DMSO ligand to the platinum(II) center. Analysis of the DMSO exchange kinetics provided for the first time a quantitative measure of the trans effect of abnormal carbene ligands. The kinetic exchange rate in these bidentate abnormal dicarbene complexes is 0.050(+/- 2) s(-1) and thus similar to analogous platinum(II) complexes containing phenylpyridine, yet significantly slower than that induced by pyridylidene pyridine. Reaction of the dicarbene platinum(II) complexes with PhICl2, Br-2 and I-2 afforded the corresponding platinum(IV) complexes. Linkage isomerism of the Pt-IV-bound DMSO was observed when the bromination reaction was performed in DMSO solution. Moreover, solvolysis was less pronounced in the platinum(IV) complexes than in the corresponding platinum(II) analogues.
Funding Details: University College Dublin
Type of material: Journal Article
Publisher: Royal Society of Chemistry
Copyright (published version): 2013 The Royal Society of Chemistry
Keywords: N-heterocyclic carbeneC-h activationMetal sulfoxide complexesOxidative additionDimethyl-sulfoxideStructural-characterizationPalladium complexesImidazoliumImidazolium saltsBond activationCoordination chemistry
DOI: 10.1039/c2dt32423g
Language: en
Status of Item: Peer reviewed
Appears in Collections:Chemistry Research Collection

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