Pure rotational spectrum and structural determination of 1,1-difluoro-1-silacyclopentane

Moon, Nicole; Marshall, F. E.; McFadden, Thomas M. C.; Ocola, Esther J.; Laane, Jaan; Guirgis, Gamil A.; Grubbs, Garry S.

doi:10.1016/j.molstruc.2021.131563

Cited by 7 publications

(4 citation statements)

References 31 publications

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“…In 1,1-difluorosilacyclohex-2-ene, however, the electronegativity of the fluorines pull electron density, causing a large shift in the Si−F hybridization of silicon to sp 3.59 and sp 3.62 , representing a large increase in p orbital contribution. This, in turn, corresponds to an increase in s contribution on the silicon atom hybridizations for Si−C(1) and Si−C (5). These hybridized orbitals are now sp 2.46 and sp 2.40 , respectively.…”

Section: The Journal Of Physical Chemistrymentioning

confidence: 95%

“…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%

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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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Section: The Journal Of Physical Chemistrymentioning

confidence: 95%

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

Self Cite

View full text Add to dashboard Cite

show abstract

“…In practice, this refers to 13 C, 15 N and 18 O, which are at approximately 1.1%, 0.36% and 0.21%, respectively, relative to the most abundant isotopes. This has been utilized to give accurate structural information for a wide variety of molecules 37–40 . However, this requires spectra with high enough sensitivity to detect these minor isotopologues, which can require long measurement runs and large sample quantities.…”

Section: Introductionmentioning

confidence: 99%

“…This has been utilized to give accurate structural information for a wide variety of molecules. 37 , 38 , 39 , 40 However, this requires spectra with high enough sensitivity to detect these minor isotopologues, which can require long measurement runs and large sample quantities. For most analytical applications, such as those described later in this Review, the agreement between experimental and computed structural parameters is sufficient to enable the molecular assignment.…”

Section: Introductionmentioning

confidence: 99%

Analysis of isomeric mixtures by molecular rotational resonance spectroscopy

Neill

Evangelisti

Pate

2023

Analytical Science Advances

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Recent developments in molecular rotational resonance (MRR) spectroscopy that have enabled its use as an analytical technique for the precise determination of molecular structure are reviewed. In particular, its use in the differentiation of isomeric compounds—including regioisomers, stereoisomers and isotopic variants—is discussed. When a mixture of isomers, such as resulting from a chemical reaction, is analyzed, it is highly desired to be able to unambiguously identify the structures of each of the components present, as well as quantify them, without requiring complex sample preparation or reference standards. MRR offers unique capabilities for addressing this analytical challenge, owing to two factors: its high sensitivity to a molecule's structure and its high spectral resolution, allowing mixtures to be resolved without separation of components. This review introduces core theoretical principles, an introduction to MRR instrumentation and the methods by which spectra can be interpreted with the aid of computational chemistry to correlate the observed patterns to molecular structures. Recent articles are discussed in which this technique was applied to help chemists complete challenging isomer analyses. Developments in the use of MRR for chiral analysis and in the measurement of isotopically labeled compounds are also highlighted.

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The chirped pulse, Fourier transform microwave spectrum of 1-chloromethyl-1-fluorosilacyclopentane

Pulliam

Marshall

Carrigan-Broda

et al. 2023

Journal of Molecular Spectroscopy

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Pure rotational spectrum and structural determination of 1,1-difluoro-1-silacyclopentane

Cited by 7 publications

References 31 publications

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

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

Analysis of isomeric mixtures by molecular rotational resonance spectroscopy

The chirped pulse, Fourier transform microwave spectrum of 1-chloromethyl-1-fluorosilacyclopentane

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