title: Microwave, r0 Structural Parameters, Conformational Stability, and Vibrational Assignment of (Chloromethyl)fluorosilane.
abstract: The FT-microwave spectrum (6.5-26 GHz) of (chloromethyl)fluorosilane (ClCH2-SiH2F) has been recorded and 250 transitions for the parent species along with (13)C, (37)Cl, (29)Si, and (30)Si isotopologues have been assigned for trans conformer. Infrared spectra (3100 to 400 cm(-1)) of gas, solid, and the variable temperature (-100 to -60 °C) studies of the infrared spectra of the sample dissolved in xenon have been recorded. Additionally, the variable temperature (-153 to -133 °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 ± 15 cm(-1) (1.47 ± 0.16 kJ mol(-1)), and in krypton solution, the enthalpy difference has been determined to be 97 ± 16 cm(-1) (1.16 ± 0.19 kJ mol(-1)) with the trans conformer as the more stable form. Approximately 46 ± 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 (Å): Si-F = 1.608 (3); C-Cl = 1.771 (3); Si-C = 1.884 (3); and angles (deg): ∠FSiC = 108.9 (5); ∠ClCSi = 104.9 (5). The results are discussed and compared to some related molecules.
authors.affiliation: Department of Chemistry and Biochemistry, College of Charleston , Charleston, South Carolina 29424, United States.
authors.forename: Gamil A
authors.initials: GA
authors.lastname: Guirgis
authors.affiliation: Department of Chemistry, University of Missouri-Kansas City , Kansas City, Missouri 64110, United States.
authors.forename: Dattatray K
authors.initials: DK
authors.lastname: Sawant
authors.affiliation: Department of Chemistry, University of Missouri-Kansas City , Kansas City, Missouri 64110, United States.
authors.forename: Reid E
authors.initials: RE
authors.lastname: Brenner
authors.affiliation: Department of Chemistry, University of Missouri-Kansas City , Kansas City, Missouri 64110, United States.
authors.forename: Bhushan S
authors.initials: BS
authors.lastname: Deodhar
authors.affiliation: Department of Chemistry, University of Virginia , Charlottesville, Virginia 22904, United States.
authors.forename: Nathan A
authors.initials: NA
authors.lastname: Seifert
authors.affiliation: Department of Chemistry, Universitair Centrum Antwerpen , 171 Groenenborglaan, Antwerpen 2020, Belgium.
authors.forename: Yannick
authors.initials: Y
authors.lastname: Geboes
authors.affiliation: Department of Chemistry, University of Virginia , Charlottesville, Virginia 22904, United States.
authors.forename: Brooks H
authors.initials: BH
authors.lastname: Pate
authors.affiliation: Department of Chemistry, Universitair Centrum Antwerpen , 171 Groenenborglaan, Antwerpen 2020, Belgium.
authors.forename: Wouter A
authors.initials: WA
authors.lastname: Herrebout
authors.affiliation: Department of Chemistry and Biochemistry, College of Charleston , Charleston, South Carolina 29424, United States.
authors.forename: Daniel V
authors.initials: DV
authors.lastname: Hickman
authors.affiliation: Department of Chemistry, University of Missouri-Kansas City , Kansas City, Missouri 64110, United States.
authors.forename: James R
authors.initials: JR
authors.lastname: Durig