Structure and bonding in cycloalkanes and monosilacycloalkanes

Boatz, Jerry A.; Gordon, Mark S.; Hilderbrandt, R. L.

doi:10.1021/ja00210a005

Cited by 54 publications

(42 citation statements)

References 1 publication

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“…155,159,160,162,163,[166][167][168][169][170][171][172][173][174][175][176][177] There is a trend of vibrational modes that are blue-shifted with correlation to ring strain in spectra of bulk cycloalkanes, which is similar to the trend observed for silane linked cycloalkanes ( Figure 6C). For four-, five-, and six-membered cycloalkanes, this stretching mode is assigned to an asymmetric C-H stretching motion on the basis of assignments made for bulk spectra, 155,159,160,162,163,[166][167][168][169][170][171][172][173][174] whereas for cylopropane, the blue-shift is so significant that the C-H stretch we observe on the silane surface is assigned as a symmetric stretch because the asymmetric stretch would occur at a frequency higher than the IR light probed in these experiments. 159,160,[175][176][177] Also notable in the silane spectra is the appearance of multiple peaks in the C-H asymmetric and symmetric stretching regions.…”

Section: Cyclic Alkanesmentioning

confidence: 55%

Pentane, Hexane, Cyclopentane, Cyclohexane, 1-Hexene, 1-Pentene,cis-2-Pentene, Cyclohexene, and Cyclopentene at Vapor/α-Alumina and Liquid/α-Alumina Interfaces Studied by Broadband Sum Frequency Generation

2009

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The molecular orientation and structure of adsorbates at oxide interfaces is driven by surface-molecule and molecule-molecule interactions and is useful for predicting reactivity and product selectivity in heterogeneous chemical reactions, including those important in catalytic processes. Using broadband vibrational sum-frequency generation spectroscopy, we probed cyclic and acyclic alkanes and olefins at buried vapor/solid and liquid/ solid interfaces of the R-alumina (0001) surface under ambient conditions. The spectroscopic signatures of the adsorbates were measured and compared with bulk phase spectra and spectra of model surfaces containing hydrocarbons covalently linked to glass slides using silane chemistry. By utilizing appropriate polarization combinations, the orientations of hydrocarbons adsorbed from the vapor were evaluated and compared to the hydrocarbon orientations at the liquid/solid interface. The data support a proposed orientation for n-alkanes and cycloalkanes at the liquid/solid interface in which the hydrocarbons lie with the planes of their carbon backbones parallel to the surface, whereas at the vapor/solid interface, the adsorbates are oriented with their carbon backbones in an orientation neither parallel nor perpendicular to the surface. The surface vibrational spectra of olefins at both types of interfaces indicate that their orientations differ from saturated counterparts, and their unique spectral signatures allow differentiation of adsorbed olefins from alkanes.

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Section: Cyclic Alkanesmentioning

confidence: 55%

Pentane, Hexane, Cyclopentane, Cyclohexane, 1-Hexene, 1-Pentene,cis-2-Pentene, Cyclohexene, and Cyclopentene at Vapor/α-Alumina and Liquid/α-Alumina Interfaces Studied by Broadband Sum Frequency Generation

2009

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“…The reaction energies of these series follow a similar trend to cycloalkanes in which (3-4)a and (3-4)b are signicantly strained, (5-7)a and (5-7)b are relatively unstrained, and (8-10) a and (8-10)b are moderately strained. [20][21][22] The longer S 1 -S 2 bond in the thiacycles relieves some strain compared the corresponding cycloalkanes (e.g., 1,2-dithiolane vs. cyclopentane).…”

Section: Resultsmentioning

confidence: 99%

Nucleophilic substitution reactions of cyclic thiosulfinates are accelerated by hyperconjugative interactions

2019

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“…Recently, there has been an increasing interest in the investigation of alternative single‐source precursor gases to replace the conventionally used mixtures of separate Si‐ (silane or chlorosilanes) and C‐containing (various hydrocarbons) gases for silicon carbide thin film formation using chemical vapor deposition (CVD) 14–17. The significant ring strain energy in the four‐membered ring structure in SCB molecules18, 19 reduces the decomposition temperatures compared with those using open‐chain alkylsilanes 14, 15. Furthermore, reactive silene and silylene species produced in the decomposition process are potentially important thin film precursors.…”

Section: Introductionmentioning

confidence: 99%

Decomposition of 1,1‐dimethyl‐1‐silacyclobutane on a tungsten filament—evidence of both ring CC and ring SiC bond cleavages

Tong¹,

Shi²

2010

J. Mass Spectrom.

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The decomposition of 1,1-dimethyl-1-silacyclobutane (DMSCB) on a heated tungsten filament has been studied using vacuum ultraviolet laser single photon ionization time-of-flight mass spectrometry. It is found that the decomposition of DMSCB on the W filament to form ethene and 1,1-dimethylsilene is a catalytic process. In addition, two other decomposition channels exist to produce methyl radicals via the Si-CH(3) bond cleavage and to form propene (or cyclopropane)/dimethylsilylene. It has been demonstrated that both the formation of ethene and that of propene are stepwise processes initiated by the cleavage of a ring C-C bond and a ring Si-C bond, respectively, to form diradical intermediates, followed by the breaking of the remaining central bonds in the diradicals. The formation of ethene via an initial cleavage of a ring C-C bond is dominant over that of propene via an initial cleavage of a ring Si-C bond. When the collision-free condition is voided, secondary reactions in the gas-phase produce various methyl-substituted 1,3-disilacyclobutane molecules. The dominant of all is found to be 1,1,3,3-tetramethyl-1,3-disilacyclobutane originated from the dimerization of 1,1-dimethylsilene.

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Structure and bonding in cycloalkanes and monosilacycloalkanes

Cited by 54 publications

References 1 publication

Pentane, Hexane, Cyclopentane, Cyclohexane, 1-Hexene, 1-Pentene,cis-2-Pentene, Cyclohexene, and Cyclopentene at Vapor/α-Alumina and Liquid/α-Alumina Interfaces Studied by Broadband Sum Frequency Generation

Pentane, Hexane, Cyclopentane, Cyclohexane, 1-Hexene, 1-Pentene,cis-2-Pentene, Cyclohexene, and Cyclopentene at Vapor/α-Alumina and Liquid/α-Alumina Interfaces Studied by Broadband Sum Frequency Generation

Nucleophilic substitution reactions of cyclic thiosulfinates are accelerated by hyperconjugative interactions

Decomposition of 1,1‐dimethyl‐1‐silacyclobutane on a tungsten filament—evidence of both ring CC and ring SiC bond cleavages

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