Broadband microwave spectroscopy of cyclopentylsilane and 1,1,1-trifluorocyclopentylsilane

Licaj, Lucas; Moon, Nicole; Grubbs, Garry S.; Guirgis, Gamil A.; Seifert, Nathan A.

doi:10.1016/j.jms.2022.111698

Cited by 4 publications

(1 citation statement)

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“…In recent years, the authors have undertaken rotational spectroscopy studies that investigate the structural differences in substituting a carbon with a silicon atom. − Studies of these systems have led to interesting physiochemical results like ring-puckering motions, planar vs nonplanar ring structures, or C 2 symmetry in straight-chain alkane species where one may expect C 2 v . In some of these systems, the potential energy surfaces of the ring-puckering motion may be flatter at the base through the puckering coordinate than the carbon analogues or may result in a double well.…”

Section: Introductionmentioning

confidence: 99%

Rotational Spectrum and Ring Structures of Silacyclohex-2-ene and 1,1-Difluorosilacyclohex-2-ene

Moon,

Duerden,

McFadden

et al. 2023

J. Phys. Chem. A

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Silacyclohex-2-ene and 1,1-difluorosilacyclohex-2-ene have been synthesized, and the chirped-pulse, Fourier-transform microwave spectra of each have been observed and analyzed from 4.9 to 23.1 GHz. Quantum chemical calculations have been performed at the B3LYP-D3BJ/Def2TZVP level of theory and predict μ a to be the largest dipole moment component with a significantly larger value in this component for 1,1-difluorosilacyclohex-2-ene. In accordance with this prediction, the spectra were predominantly a-type with the observation of a few b-and c-type transitions. The signalto-noise ratio was adequate in both spectra to observe 29 Si, 30 Si, and all singly substituted 13 C isotopologues in natural abundance. All spectra have been fit to a semirigid rotational Hamiltonian and are presented. Analysis of the physical meaning of the fitted parameters is explored and determined to hold for the rotational constants while being more empirical for the centrifugal distortion terms. Experimental structures of both molecules indicate that the quantum chemically calculated structures for the atoms in the ring are a very close depiction of the experimentally determined structures. The structures of each molecule are compared to similar molecules for context, where it is shown that both molecules possess a similar "half-chair" conformation to that of the all-carbon analogue, cyclohexene.

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