Intramolecularly Stabilised Group 10 Metal Stannyl and Stannylene Complexes: Multi‐pathway Synthesis and Observation of Platinum‐to‐Tin Alkyl Transfer |
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| Authors: | Cornelis A. Boon Dr. Yves Cabon Dr. Jeroen J. M. de Pater Dr. Martin Lutz Prof. Dr. Robertus J. M. Klein Gebbink Prof. Dr. Berth‐Jan Deelman |
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| Affiliation: | 1. Organic Chemistry and Catalysis, Debye Institute for Nanomaterial Science, Faculty of Science, Utrecht University, Universiteitsweg 99, 3584 CG Utrecht (The Netherlands);2. ARKEMA B.V. Location Vlissingen, P.O. Box 70, 4380 AB Vlissingen (The Netherlands);3. Crystal and Structural Chemistry, Bijvoet Center for Biomolecular Research, Faculty of Science, Utrecht University, Padualaan 8, 3584 CH Utrecht (The Netherlands) |
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| Abstract: | Reaction of [PdClMe(P^N)2] with SnCl2 followed by Cl‐abstraction leads to apparent Pd?C bond activation, resulting in methylstannylene species trans‐[PdCl{(P^N)2SnClMe}][BF4] (P^N=diaryl phosphino‐N‐heterocycle). In contrast, reaction of Pt analogues with SnCl2 leads to Pt?Cl bond activation, resulting in methylplatinum species trans‐[PtMe{(P^N)2SnCl2}][BF4]. Over time, they isomerise to methylstannylene species, indicating that both kinetic and thermodynamic products can be isolated for Pt, whereas for Pd only methylstannylene complexes are isolated. Oxidative addition of RSnCl3 (R=Me, Bu, Ph) to M0 precursors (M=Pd or Pt) in the presence of P^N ligands results in diphosphinostannylene pincer complexes trans‐[MCl{(P^N)2SnCl(R)}][SnCl4R], which are structurally similar to the products from SnCl2 insertion. This showed that addition of RSnCl3 to M0 results in formal Sn?Cl bond oxidative addition. A probable pathway of activation of the tin reagents and formation of different products is proposed and the relevancy of the findings for Pd and Pt catalysed processes that use SnCl2 as a co‐catalyst is discussed. |
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| Keywords: | alkyl transfer metal– metal interactions palladium platinum tin |
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