Abstract

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 μa 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 signal-to-noise ratio was adequate in both spectra to observe 29Si, 30Si, and all singly substituted 13C 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.

Department(s)

Chemistry

Comments

National Science Foundation, Grant CHE-MRI-2019072

International Standard Serial Number (ISSN)

1520-5215; 1089-5639

Document Type

Article - Journal

Document Version

Citation

File Type

text

Language(s)

English

Rights

© 2024 American Chemical Society, All rights reserved.

Publication Date

11 Jan 2024

PubMed ID

38159057

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Chemistry Commons

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