Untersuchungen zur Thermolyse von Si2OCl6 / Thermolysis of Si2OCl6

Wilkening, Andreas; Binnewies, Michael

doi:10.1515/znb-2000-0105

Cited by 6 publications

(2 citation statements)

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“…They further performed DFT calculations to compare the thermochemical properties of SiOCl 2 . In another recent study, higher chlorosiloxanes were formed by the thermolysis of Si 2 OCl 6 and involvement of SiOCl 2 has been emphasized for the larger chlorosiloxane growth …”

Section: Introductionmentioning

confidence: 97%

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Reaction Mechanism of Chlorosiloxane Ring Formation from SiCl₄ and O₂

2002

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The formation of the chlorosiloxane ring (Cl 2 SiO) 2 from the reaction of SiCl 4 with O 2 has been studied using density functional theory (DFT). Geometries of reactants, intermediates, transition states, and products were fully optimized, and the relative energies of the stationary points and all of the transition states were calculated on the B3LYP/6-311G* level. The initial reaction of O 2 with SiCl 4 starts on the triplet surface with the insertion of O 2 in SiCl 4 . This will loosen one Cl atom, and a barrier of 56.6 kcal/mol must be overcome. In the next step Cl 2 is eliminated and the cyclic-Cl 2 SiO 2 is formed. The latter reacts with SiCl 4 , which involves a barrier of 76.0 kcal/mol. This process leads to the formation of a low-lying intermediate Cl 2 SiO(OCl)SiCl 3 . The intermediate proceeds under elimination of Cl 2 to the product (Cl 2 SiO) 2 ring over a barrier of 71.3 kcal/ mol. This study also shows that the formation of the Cl 3 SiO radical is found to be energetically more favorable than that of Cl 2 SiO. This can lead to the growth of larger chlorosiloxanes.

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Section: Introductionmentioning

confidence: 97%

“…With the availability of SiOCl 2 , one could imagine that the following reactions lead to the chlorosiloxane chain and ring formation: Wilkening and Binnewies proposed the formation of higher condensed siloxanes via SiCl 4 elimination. However, they could not identify the presence of SiOCl 2 using a mass spectrometer.…”

Section: Introductionmentioning

confidence: 99%