Molecular Structures of Acetylene Derivatives of Tin. VIII Trimethylstannylacetylene: Use of Results of Quantum-Chemical Calculations and Spectroscopic Measurements in Analysis of Gas-Phase Electron Diffraction Data

Khaikin, L. S.; Grikina, O. E.; Granovsky, A. A.; Никитин, В. С.; Vilkov, L. V.

doi:10.1023/b:stuc.0000010465.23794.d0

Cited by 4 publications

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References 23 publications

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“…As can be seen, the determined parameters of the nonrigid −CH 2 −CH 2 − fragment are different from those calculated at the MP2(full)/6−311G(3df,2p) level, whereas the parameters of the rigid part are in good agreement. The large differences between the rms vibrational amplitudes u h1 and those calculated in the traditional approximation u h0 (0.006 and 0.013 Å for the =C...C and C...O(f) terms, respectively) point also to the nonrigidity of the molecular fragment . The radial distribution curve f ( r ) shows also remarkable discrepancies between the experimental and theoretical curves in the ranges of the C−C, =C...C, C...O(n), and C...O(f) and other distances between the atoms involved in the large-amplitude ring-twisting motion (see Figure ; for definition of the C...O(f) and C...O(n) distances, see footnote b to Table ).…”

Section: Analysis Of the Ged Data Supplemented By Results Of Ab Initi...mentioning

confidence: 88%

“…The large differences between the rms vibrational amplitudes u h1 and those calculated in the traditional approximation u h0 (0.006 and 0.013 Å for the )C...C and C...O(f) terms, respectively) point also to the nonrigidity of the molecular fragment. 35 The radial distribution curve f(r) shows also remarkable discrepancies between the experimental and theoretical curves in the ranges 3).…”

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confidence: 97%

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Flexibility of the Saturated Five-Membered Ring in 2,5-Pyrrolidinedione (Succinimide): Electron Diffraction and Quantum-Chemical Studies with Use of Vibrational Spectroscopy Data

et al. 2009

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The flexibility of succinimide molecule has been studied for the first time by quantum-chemical (at the MP2 level with up to the 6-311G(3df,2p) basis sets) and gas-phase electron diffraction (GED) methods using vibrational spectroscopy data from literature. The analysis of vibrational spectra, performed for the molecular model of C(2v) symmetry (predicted by high-level ab initio calculations) using the scaling procedure, has shown that the two out-of-plane ring motions, that is, ring-bending and ring-twisting, are practically pure modes of different symmetry types and can be considered separately. The one-dimensional potential curves for the ring-bending and ring-twisting vibrations calculated at the MP2(full)/6-311G(3df,2p) level could be approximated by harmonic and anharmonic functions, respectively. The diverged energy levels for the ring-twisting vibration and the constant transition frequencies for the bending motion, obtained by the solution of the direct one-dimensional problem for the nonrigid model, demonstrate this statement. In the GED analysis, the succinimide molecule with a large-amplitude ring-twisting motion was described by a dynamic model with the distribution of pseudoconformers according to the calculated potential function taking into account structural relaxation effects from the MP2(full)/6-311G(3df,2p) calculations. This model greatly improved the fit of the GED intensities (R factor decreased from 4.6% for static model to 2.8%). The equilibrium molecular parameters r(e) determined in the dynamic approximation are very close to the corresponding values from the ab initio calculations. At the same time, the parameters of the -CH(2)-CH(2)- fragment involved in the ring-twisting motion deviate considerably from those obtained for the static model (C-C bond length by 0.027 A, =C-C-H, C-C-H, and H-C-C-N angles by up to 7 degrees). The flexibility influence on the C-C bond length is several times larger than the calculated vibrational correction (r(e) - r(a)) as well as the experimental uncertainty.

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Section: Analysis Of the Ged Data Supplemented By Results Of Ab Initi...mentioning

confidence: 88%

mentioning

confidence: 97%

Flexibility of the Saturated Five-Membered Ring in 2,5-Pyrrolidinedione (Succinimide): Electron Diffraction and Quantum-Chemical Studies with Use of Vibrational Spectroscopy Data

et al. 2009

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“…Considerable progress has been made in the last decade toward the synthesis of primary α,β- and β,γ-unsaturated germanes and stannanes. , Some experimental gas-phase structures of organogermanes such as germane and halogenated germanes, − ethynylgermane, methylgermane, ethylgermane, ethylchlorogermane, cyclopropylgermane, vinylgermane, (halomethyl)germane, , and propargylgermane and organostannanes such as stannane, trimethylstannylacetylene, , methylstannane bis(trimethylstannyl)acetylene, tetramethyltin, and tetraethynyltin 28 have been determined. The first structural studies of vinylstannane and allylstannane 29 will be published shortly.…”

Section: Introductionmentioning

confidence: 99%

Structures of 1,2-Propadienylgermane (Allenylgermane) and 1,2-Propadienylstannane (Allenylstannane) Determined by Gas-Phase Electron Diffraction and Quantum Chemical Calculations

et al. 2006

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“…In the next paper, Khaiikin et al [11] discussed trimethylstannylacetylene. How much conjugative stabilization arises from adjacent stannyl and alkyne moieties?…”

Section: Introductionmentioning

confidence: 97%

Interplay of thermochemistry and structural chemistry, the journal (volume 15, 2004) and the discipline

Stem

Liebman

2006

Struct Chem

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As practiced disciplines, structural chemistry, and thermochemistry need not necessarily be related. Yet such relationships, ranging from minor to very close, can help our overall understanding and detailed analyses of the species and methods under consideration. In the current study, these relations are made more evident from among the contents of the journal "Structural Chemistry" (Vol. 15) for the year 2004. The year's articles have been reviewed, giving to most of those appearing therein a thermochemical commentary, "spin" or "slant." A special emphasis is made on raising questions or noting possible future research topics that arise when looking at the relations noted earlier.

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Molecular Structures of Acetylene Derivatives of Tin. VIII Trimethylstannylacetylene: Use of Results of Quantum-Chemical Calculations and Spectroscopic Measurements in Analysis of Gas-Phase Electron Diffraction Data

Cited by 4 publications

References 23 publications

Flexibility of the Saturated Five-Membered Ring in 2,5-Pyrrolidinedione (Succinimide): Electron Diffraction and Quantum-Chemical Studies with Use of Vibrational Spectroscopy Data

Flexibility of the Saturated Five-Membered Ring in 2,5-Pyrrolidinedione (Succinimide): Electron Diffraction and Quantum-Chemical Studies with Use of Vibrational Spectroscopy Data

Structures of 1,2-Propadienylgermane (Allenylgermane) and 1,2-Propadienylstannane (Allenylstannane) Determined by Gas-Phase Electron Diffraction and Quantum Chemical Calculations

Interplay of thermochemistry and structural chemistry, the journal (volume 15, 2004) and the discipline

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