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Intramolecularly Stabilised Group 10 Metal Stannyl and Stannylene Complexes: Multi‐pathway Synthesis and Observation of Platinum‐to‐Tin Alkyl Transfer
Author(s) -
Warsink Stefan,
Derrah Eric J.,
Boon Cornelis A.,
Cabon Yves,
de Pater Jeroen J. M.,
Lutz Martin,
Klein Gebbink Robertus J. M.,
Deelman BerthJan
Publication year - 2015
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201404071
Subject(s) - chemistry , pincer movement , medicinal chemistry , alkyl , tin , oxidative addition , catalysis , metal , reagent , stereochemistry , reductive elimination , platinum , organic chemistry
Reaction of [PdClMe(P^N) 2 ] with SnCl 2 followed by Cl‐abstraction leads to apparent PdC bond activation, resulting in methylstannylene species trans ‐[PdCl{(P^N) 2 SnClMe}][BF 4 ] (P^N=diaryl phosphino‐N‐heterocycle). In contrast, reaction of Pt analogues with SnCl 2 leads to PtCl bond activation, resulting in methylplatinum species trans ‐[PtMe{(P^N) 2 SnCl 2 }][BF 4 ]. 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 RSnCl 3 (R=Me, Bu, Ph) to M 0 precursors (M=Pd or Pt) in the presence of P^N ligands results in diphosphinostannylene pincer complexes trans ‐[MCl{(P^N) 2 SnCl(R)}][SnCl 4 R], which are structurally similar to the products from SnCl 2 insertion. This showed that addition of RSnCl 3 to M 0 results in formal SnCl 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 SnCl 2 as a co‐catalyst is discussed.