Microwave, r0 Structural Parameters, Conformational Stability, and Vibrational Assignment of (Chloromethyl)fluorosilane

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• 作者：Gamil A. Guirgis ; Dattatray K. Sawant ; Reid E. Brenner ; Bhushan S. Deodhar ; Nathan A. Seifert ; Yannick Geboes ; Brooks H. Pate ; Wouter A. Herrebout ; Daniel V. Hickman ; James R. Durig
• 刊名：Journal of Physical Chemistry A
• 出版年：2015
• 出版时间：November 25, 2015
• 年：2015
• 卷：119
• 期：47
• 页码：11532-11547
• 全文大小：438K
• ISSN：1520-5215

文摘

The FT-microwave spectrum (6.5鈥?6 GHz) of (chloromethyl)fluorosilane (ClCH₂鈥揝iH₂F) has been recorded and 250 transitions for the parent species along with ¹³C, ³⁷Cl, ²⁹Si, and ³⁰Si isotopologues have been assigned for trans conformer. Infrared spectra (3100 to 400 cm^鈥?) of gas, solid, and the variable temperature (鈭?00 to 鈭?0 掳C) studies of the infrared spectra of the sample dissolved in xenon have been recorded. Additionally, the variable temperature (鈭?53 to 鈭?33 掳C) studies of the Raman spectra of the sample dissolved in krypton have been recorded. The enthalpy difference between the trans and gauche conformers in xenon solutions has been determined to be 109 卤 15 cm^鈥? (1.47 卤 0.16 kJ mol^鈥?), and in krypton solution, the enthalpy difference has been determined to be 97 卤 16 cm^鈥? (1.16 卤 0.19 kJ mol^鈥?) with the trans conformer as the more stable form. Approximately 46 卤 2% of the trans form is present at ambient temperature. By utilizing the microwave rotational constants of five isotopologues for trans and the structural parameters predicted from MP2(full)/6-311+G(d,p) calculations, adjusted r₀ parameters have been obtained for trans conformer. The r₀ structural parameter values for the trans form are for the heavy atom distances (脜): Si鈥揊 = 1.608 (3); C鈥揅l = 1.771 (3); Si鈥揅 = 1.884 (3); and angles (deg): 鈭燜SiC = 108.9 (5); 鈭燙lCSi = 104.9 (5). The results are discussed and compared to some related molecules.