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

被引:26
作者
Becerra, R
Goldberg, N
Cannady, JP
Almond, MJ
Ogden, JS
Walsh, R [1 ]
机构
[1] Univ Reading, Sch Chem, Reading RG6 6AD, Berks, England
[2] CSIC, Inst Quim Fis Rocasolano, E-28006 Madrid, Spain
[3] Dow Corning Corp, Midland, MI 48686 USA
[4] Univ Southampton, Dept Chem, Southampton SO17 1BJ, Hants, England
关键词
D O I
10.1021/ja049373g
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
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.
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页码:6816 / 6824
页数:9
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