Reactions of SiCl2 with N2O, NO and O2

Goldberg, Nicola; Ogden, J. S.; Almond, Matthew J.; Walsh, Robin; Cannady, J. Pat; Becerra, Rosa; Lee, Jennifer A.

doi:10.1039/b309871k

Cited by 18 publications

(12 citation statements)

References 27 publications

(40 reference statements)

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“…Despite significant deactivation effect of two halogen atoms, which will be discussed below, the reaction of SiHal 2 with 1,3-dienes retains its major importance as a reliable proof for formation of these intermediates in reaction mixture. One of the latest examples of this is provided by Goldberg et al [26].…”

Section: H 6 Esihal 2 (Hal ¼ F Cl) Systemsmentioning

confidence: 95%

Computational study of reaction pathways in the course of interaction of deactivated silylenes with buta-1,3-diene

Rynin

Faustov

Боганов

et al. 2010

Journal of Organometallic Chemistry

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Section: H 6 Esihal 2 (Hal ¼ F Cl) Systemsmentioning

confidence: 95%

Computational study of reaction pathways in the course of interaction of deactivated silylenes with buta-1,3-diene

Rynin

Faustov

Боганов

et al. 2010

Journal of Organometallic Chemistry

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“…In an earlier study of SiCl 2 with O 2 , 16 we have calculated parts of the analogous PES to that for SiH 2 þ O 2 . The main similarity is the importance of cyclo-Cl 2 SiO 2 as a crucial intermediate.…”

Section: Other Mechanistic Comparisonsmentioning

confidence: 99%

“…15 A further interest to us was to compare the behaviour towards O 2 of SiH 2 and SiCl 2 , which we have studied by end product analysis. 16 The reaction of SiH 2 with O 2 is likely, initially, to form an acyclic adduct in the triplet state, 17 viz.…”

Section: Introductionmentioning

confidence: 99%

Time-resolved gas-phase kinetic and quantum chemical studies of the reaction of silylene with oxygen

Becerra

Bowes

Ogden

et al. 2005

Phys. Chem. Chem. Phys.

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Time-resolved kinetic studies of the reaction of silylene, SiH2, generated by laser flash photolysis of phenylsilane, have been carried out to obtain rate constants for its bimolecular reaction with O(2). The reaction was studied in the gas phase over the pressure range 1-100 Torr in SF(6) bath gas, at five temperatures in the range 297-600 K. The second order rate constants at 10 Torr were fitted to the Arrhenius equation: [see text] The decrease in rate constant values with increasing temperature, although systematic is very small. The rate constants showed slight increases in value with pressure at each temperature, but this was scarcely beyond experimental uncertainty. From estimates of Lennard-Jones collision rates, this reaction is occurring at ca. 1 in 20 collisions, almost independent of pressure and temperature. Ab initio calculations at the G3 level backed further by multi-configurational (MC) SCF calculations, augmented by second order perturbation theory (MRMP2), support a mechanism in which the initial adduct, H(2)SiOO, formed in the triplet state (T), undergoes intersystem crossing to the more stable singlet state (S) prior to further low energy isomerisation processes leading, via a sequence of steps, ultimately to dissociation products of which the lowest energy pair are H2O+SiO. The decomposition of the intermediate cyclo-siladioxirane, via O-O bond fission, plays an important role in the overall process. The bottleneck for the overall process appears to be the T-->S process in H2SiOO. This process has a small spin-orbit coupling matrix element, consistent with an estimate of its rate constant of 1x10(9) s-1 obtained with the aid of RRKM theory. This interpretation preserves the idea that, as in its reactions in general, SiH2 initially reacts at the encounter rate with O2. The low values for the secondary reaction barriers on the potential energy surface account for the lack of an observed pressure dependence. Some comparisons are drawn with the reactions of CH2+O2 and SiCl2+O2.

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“…The mass spectrum of Si 2 Cl 6 has been discussed elsewhere. 24,25 When a gaseous mixture of Si 2 Cl 6 (1 Torr) and CH 3 OH (1 Torr) was mixed for 3 h then flowed into the mass spectrometer, peaks were seen in the mass spectrum which were assigned to the ions:…”

Section: Reactions Of Si 2 CL 6 With Methanol and Ethanolmentioning

confidence: 99%

The gas-phase reactions of SiCl4 and Si2Cl6 with CH3OH and C2H5OH: An investigation by mass spectrometry and matrix-isolation infrared spectroscopy

Goldberg

Almond

Ogden

et al. 2004

Phys. Chem. Chem. Phys.

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The gas phase reactions of SiCl 4 and Si 2 Cl 6 with CH 3 OH and C 2 H 5 OH have been investigated using both mass spectrometry and matrix isolation techniques. SiCl 4 reacts with both CH 3 OH and C 2 H 5 OH upon mixing of the vapours for times in excess of 3 h to generate the HCl-elimination products SiCl 3 OR (R ¼ CH 3 or C 2 H 5 ). The identity of these products is confirmed by deuteration experiments and by ab initio calculations at the HF/6-31G(d) level. Further products are generated when the mixture is passed through a tube heated to 750 C. Si 2 Cl 6 reacts with CH 3 OH and C 2 H 5 OH via a different mechanism in which the Si-Si bond is cleaved to yield SiCl 3 OR and HCl. Other products of the type SiCl 4Àn (OCH 3 ) n are tentatively identified by a combination of mass spectrometric and matrix isolation measurements. These latter products indicate further replacement of Cl atoms by OR groups as a result of reaction of CH 3 OH or C 2 H 5 OH with the initial product.

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Reactions of SiCl2 with N2O, NO and O2

Cited by 18 publications

References 27 publications

Computational study of reaction pathways in the course of interaction of deactivated silylenes with buta-1,3-diene

Computational study of reaction pathways in the course of interaction of deactivated silylenes with buta-1,3-diene

Time-resolved gas-phase kinetic and quantum chemical studies of the reaction of silylene with oxygen

The gas-phase reactions of SiCl4 and Si2Cl6 with CH3OH and C2H5OH: An investigation by mass spectrometry and matrix-isolation infrared spectroscopy

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