From a Zwitterionic Phosphasilene to Base Stabilized Silyliumylidene-Phosphide and Bis(silylene) Complexes.
The reactivity of ylide-like phosphasilene 1 [LSi(TMS)═P(TMS), L = PhC(NtBu)] with group 10 d10 transition metals is reported. For the first time, a reaction of a phosphasilene with a transition metal that actually involves the silicon–phosphorus double bond was found. In the reaction of 1 with ethy...
| Publicado en: | Journal of the American Chemical Society Vol. 135; no. 47; pp. 17958 - 17969 |
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| Autores principales: | , , , , |
| Formato: | Artículo |
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American Chemical Society
11/27/2013
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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=92977791&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 92977791 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: 11/27/2013 vid: 135 iid: 47 pid: 997 pub: American Chemical Society artinfo: ui: 92977791 10.1021/ja409720c ppf: 17958 ppct: 11 formats: tig: atl: From a Zwitterionic Phosphasilene to Base Stabilized Silyliumylidene-Phosphide and Bis(silylene) Complexes. aug: au: Breit, Nora C. Szilvási, Tibor Tsuyoshi Suzuki Gallego, Daniel Shigeyoshi Inoue affil: Institut für Chemie, Technische Universität Berlin, Straße des 17. Juni 135, Sekr. C2, D-10623 Berlin, Germany Department of Inorganic and Analytical Chemistry, Budapest University of Technology and Economics, Szent Gellért tér 4, 1111 Budapest, Hungary su: Phosphorus Transition metals Silicon research Nickel Density functionals Palladium sug: subj: Phosphorus Transition metals Silicon research Nickel Density functionals Palladium ab: The reactivity of ylide-like phosphasilene 1 [LSi(TMS)═P(TMS), L = PhC(NtBu)] with group 10 d10 transition metals is reported. For the first time, a reaction of a phosphasilene with a transition metal that actually involves the silicon–phosphorus double bond was found. In the reaction of 1 with ethylene bis(triphenylphosphine) platinum(0), a complete silicon–phosphorus bond breakage occurs, yielding the unprecedented dinuclear platinum complex 3 [LSi{Pt(PPh)}P(TMS)]. Spectroscopic, structural, and theoretical analysis of complex 3 revealed the cationic silylene (silyliumylidene) character of the silicon unit in complex 3. Similarly, formation of the analogous dinuclear palladium complex 4 [LSi{Pd(PPh)}P(TMS)] from tetrakis(triphenylphosphine) palladium(0) was observed. On the other hand, in the case of bis(cyclooctadiene) nickel(0) as starting material, a distinctively different product, the bis(silylene) nickel complex 5 [{(LSi)P(TMS)}Ni(COD)], was obtained. Complex 5 was fully characterized including X-ray diffraction analysis. Density functional theory calculations of the reaction mechanisms showed that the migration of the TMS group in the case of platinum and palladium was induced by the oxidative addition of the transition metal into the silicon–silicon bond. The respective platinum intermediate 2 [LSi{Pt(TMS)(PPh)}P(TMS)] was also experimentally observed. This is contrasted by the reaction of nickel, in which the equilibrium of phosphasilene 1 and the phosphinosilylene 6 [LSiP(TMS)] was utilized for a better coordination of the silicon(II) moiety in comparison with phosphorus to the transition metal center. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2013 holdings: @attributes: islocal: N |
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