Reaction Mechanism of Chlorosiloxane Ring Formation from SiCl_4 and O_2

Anil Kumar; Thorsten Homann; Karl Jug

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Reaction Mechanism of Chlorosiloxane Ring Formation from SiCl_4 and O_2

机译：由SiCl_4和O_2形成氯硅氧烷环的反应机理

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The formation of the chlorosiloxane ring (Cl_2SiO)_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_2SiO_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_2SiO(OCl)SiCl_3. The intermediate proceeds under elimination of Cl_2 to the product (Cl_2SiO)_2 ring over a barrier of 71.3 kcal/mol. This study also shows that the formation of the Cl_3SiO radical is found to be energetically more favorable than that of Cl_2SiO. This can lead to the growth of larger chlorosiloxanes.

机译：利用密度泛函理论（DFT）研究了SiCl_4与O_2反应形成氯硅氧烷环（Cl_2SiO）_2的过程。充分优化了反应物，中间体，过渡态和产物的几何形状，并在B3LYP / 6-311G〜*的水平上计算了固定点和所有过渡态的相对能量。 O_2与SiCl_4的初始反应从OCl插入SiCl_4的三重态表面开始。这将使一个Cl原子松动，必须克服56.6 kcal / mol的势垒。在下一步中，Cl_2被消除并且形成环状的Cl_2SiO_2。后者与SiCl_4反应，后者的势垒为76.0 kcal / mol。此过程导致形成低洼的中间体Cl_2SiO（OCl）SiCl_3。在消除Cl_2至产物（Cl_2SiO）_2环的过程中，中间体以71.3kcal / mol的势垒进行。这项研究还表明，发现Cl_3SiO自由基的形成在能量上比Cl_2SiO更有利。这可能导致较大的氯硅氧烷的生长。

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《The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory》 |2002年第29期|共8页
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Anil Kumar; Thorsten Homann; Karl Jug;
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中图分类物理化学（理论化学）、化学物理学;
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1. Reaction Mechanism of Chlorosiloxane Ring Formation from SiCl_4 and O_2 [J] . Anil Kumar, Thorsten Homann, Karl Jug The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory . 2002,第29期

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Reaction Mechanism of Chlorosiloxane Ring Formation from SiCl_4 and O_2

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