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Título: | A Cationic Unsaturated Platinum(II) Complex that Promotes the Tautomerization of Acetylene to Vinylidene |
Autor: | Ortega-Moreno, Laura; Peloso, Riccardo CSIC ORCID; López-Serrano, Joaquín CSIC ORCID CVN; Iglesias-Sigüenza, Javier; Maya, Celia CSIC ORCID; Carmona, Ernesto CSIC ORCID | Fecha de publicación: | 2017 | Editor: | Wiley-VCH | Citación: | Angewandte Chemie International Edition 56: 2772- 2775 (2017) | Resumen: | Complex [PtMe(PMeAr)] (1), which contains a tethered terphenyl phosphine (Ar =2,6-(2,6-PrCH)CH), reacts with [H(EtO)]BAr (BAr =B[3,5-(CF)CH] ) to give the solvent (S) complex [PtMe(S)(PMeAr)] (2⋅S). Although the solvent molecule is easily displaced by a Lewis base (e.g., CO or CH) to afford the corresponding adducts, treatment of 2⋅S with CH yielded instead the allyl complex [Pt(η-CH)(PMeAr)] (6) via the alkyne intermediate [PtMe(η-CH)(PMeAr )] (5). Deuteration experiments with CD, and kinetic and theoretical investigations demonstrated that the conversion of 5 into 6 involves a Pt-promoted HC≡CH to :C=CH tautomerization in preference over acetylene migratory insertion into the Pt−Me bond. | URI: | http://hdl.handle.net/10261/148670 | DOI: | 10.1002/anie.201700087 | Identificadores: | doi: 10.1002/anie.201700087 issn: 1521-3773 |
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