Experimental and theoretical evidence for homogeneous catalysis in the gas-phase reaction of SiH2 with H2O (and D2O): a combined kinetic and quantum chemical study
Becerra, Rosa, Goldberg, Nicola, Cannady, J. Pat, Almond, Matthew J., Ogden, J. Steven and Walsh, Robin (2004) Experimental and theoretical evidence for homogeneous catalysis in the gas-phase reaction of SiH2 with H2O (and D2O): a combined kinetic and quantum chemical study. Journal of the American Chemical Society, 126, (21), 6816-6824. (doi: 10.1021/ja049373g).
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Time-resolved kinetic studies of the reaction of silylene, SiH2, with H2O and with D2O have been carried out in the gas phase at 297 K and at 345 K, using laser flash photolysis to generate and monitor SiH2. The reaction was studied independently as a function of H2O (or D2O) and SF6 (bath gas) pressures. At a fixed pressure of SF6 (5 Torr), [SiH2] decay constants, k(obs), showed a quadratic dependence on [H2O] or [D2O]. At a fixed pressure of H2O or D2O, k(obs) Values were strongly dependent on [SF6]. The combined rate expression is consistent with a mechanism involving the reversible formation of a vibrationally excited zwitterionic donor-acceptor complex, H2Si...OH2 (or H2Si...OD2). This complex can then either be stabilized by SF6 or it reacts with a further molecule of H2O (or D2O) in the rate-determining step. Isotope effects are in the range 1.0-1.5 and are broadly consistent with this mechanism. The mechanism is further supported by RRKM theory, which shows the association reaction to be close to its third-order region of pressure (SF6) dependence. Ab initio quantum calculations, carried out at the G3 level, support the existence of a hydrated zwitterion H2Si...(OH2)(2), which can rearrange to hydrated silanol, with an energy barrier below the reaction energy threshold. This is the first example of a gas-phase-catalyzed silylene reaction.
|Keywords:||silylene addition-reaction, potential-energy surface, absolute rate constants, temperature-dependence, ab-initio, silicon-hydrogen, oxygen-hydrogen, prototype, bonds, dimethylsilylene|
|Subjects:||Q Science > QD Chemistry|
|Divisions:||University Structure - Pre August 2011 > School of Chemistry
|Date Deposited:||23 Feb 2006|
|Last Modified:||31 May 2011 23:31|
|Contributors:||Becerra, Rosa (Author)
Goldberg, Nicola (Author)
Cannady, J. Pat (Author)
Almond, Matthew J. (Author)
Ogden, J. Steven (Author)
Walsh, Robin (Author)
|Date:||2 June 2004|
|RDF:||RDF+N-Triples, RDF+N3, RDF+XML, Browse.|
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