Non-Metal-Catalyzed Heterodehydrocoupling of Phosphines and Hydrosilanes: Mechanistic Studies of B(CF)-Mediated Formation of P-Si Bonds.
Non-metal-catalyzed heterodehydrocoupling of primary and secondary phosphines (RRPH, R = H or R) with hydrosilanes (RRRSiH, R, R = H or R) to produce synthetically useful silylphosphines (RRP-SiRRR) has been achieved using B(CF) as the catalyst (10 mol %, 100 °C). Kinetic studies demonstrated that t...
| Publicado en: | Journal of the American Chemical Society Vol. 139; no. 46; pp. 16780 - 16791 |
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| Autores principales: | , , , , |
| Formato: | Artículo |
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American Chemical Society
11/22/2017
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| Materias: | |
| Acceso en línea: | Ver este registro en EBSCOhost |
| fields | @attributes: recordID: 1 pdfLink: plink: https://search.ebscohost.com/login.aspx?direct=true&db=hlh&AN=126507532&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 126507532 longDbName: Humanities International Complete uiTag: AN controlInfo: bkinfo: jinfo: jid: 00027863 ACS jtl: Journal of the American Chemical Society issn: 00027863 maglogo: N pubinfo: dt: 11/22/2017 vid: 139 iid: 46 pid: 997 pub: American Chemical Society artinfo: ui: 126507532 10.1021/jacs.7b09175 ppf: 16780 ppct: 11 formats: tig: atl: Non-Metal-Catalyzed Heterodehydrocoupling of Phosphines and Hydrosilanes: Mechanistic Studies of B(CF)-Mediated Formation of P-Si Bonds. aug: au: Lipeng Wu Chitnis, Saurabh S. Haijun Jiao Annibale, Vincent T. Manners, Ian affil: School of Chemistry, University of Bristol, Cantock s Close, Bristol, BS8 1TS, United Kingdom Leibniz-Institut fur Katalyse e. V., Albert-Einstein-Straße 29a, 18059 Rostock, Germany su: Phosphines Silane Chemical reactions Density functional theory Chemical bonds Nucleophilic reactions sug: subj: Phosphines Silane Chemical reactions Density functional theory Chemical bonds Nucleophilic reactions ab: Non-metal-catalyzed heterodehydrocoupling of primary and secondary phosphines (RRPH, R = H or R) with hydrosilanes (RRRSiH, R, R = H or R) to produce synthetically useful silylphosphines (RRP-SiRRR) has been achieved using B(CF) as the catalyst (10 mol %, 100 °C). Kinetic studies demonstrated that the reaction is first-order in hydrosilane and B(CF) but zero-order in phosphine. Control experiments, DFT calculations, and DOSY NMR studies suggest that a RRHPB(CF) adduct is initially formed and undergoes partial dissociation to form an "encounter complex". The latter mediates frustrated Lewis pair type Si-H bond activation of the silane substrates. We also found that B(CF) catalyzes the homodehydrocoupling of primary phosphines to form cyclic phosphine rings and the first example of a non-metal-catalyzed hydrosilylation of P-P bonds to produce silylphosphines (RRP-SiRRR). Moreover, the introduction of PhCN to the reactions involving secondary phosphines with hydrosilanes allowed the heterodehydrocoupling reaction to proceed efficiently under much milder conditions (1.0 mol % B(CF) at 25 °C). Mechanistic studies, as well as DFT calculations, revealed that PhCN plays a key mechanistic role in facilitating the dehydrocoupling reactions rather than simply functioning as H-acceptor. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2017 holdings: @attributes: islocal: N |
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