Gas-phase structures of di-t-butyl ether and t-butyl methyl ether

Liedle, Siegfried; Mack, Hans‐Georg; Oberhammer, Heinz; Imam, Mita R.; Allinger, Norman L.

doi:10.1016/0022-2860(89)80025-0

Cited by 24 publications

(17 citation statements)

References 28 publications

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“…1.42 Å), except for the tert -butyl ether, which possesses a longer bond of 1.445(10) Å. A similar lengthening of O−C bonds has been observed between Me 2 O (1.415(1) Å) and ( t -Bu) 2 O (1.436(4) Å) . The CC−O angles are larger (126−128°) in the syn structures than those in the anti forms (120−123°).…”

Section: Discussionsupporting

confidence: 57%

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Gas-Phase Structures and Conformational Properties of tert-Butyl Vinyl Ether and (Z)-Methyl 1-Propenyl Ether

Leibold

Oberhammer

1998

J. Am. Chem. Soc.

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The gas-phase structures of tert-butyl vinyl ether, t-BuOC(H)CH2 (t-BVE), and (Z)-methyl 1-propenyl ether, MeOC(H)C(H)Me (Z-MPE), have been studied by gas electron diffraction and ab initio calculations (HF/3-21G and MP2/6-31G*). For both compounds only a single conformer with a slightly nonplanar anti structure of the CC−O−C skeleton was observed. The vibrationally averaged dihedral angles φ(CC−O−C) are 167(5)° (t-BVE) and 161(5)° (Z-MPE), respectively. The experimental scattering intensities are fitted slightly better with dynamic models and double minimum potentials for the internal rotation around the O−C(sp2) bonds. The dihedral angles of the equilibrium structures φe(CC−O−C) are 170(5)° for t-BVE and 161(8)° for Z-MPE. The potential barriers at the exactly planar anti conformation (φ(CC−O−C)=180°) are V 0 = 0.15(10) and 0.20(10) kcal mol-1, respectively. The experimental results are reproduced very well by MP2/6-31G* calculations (φe = 169.0° and 154.2° and V 0 = 0.12 and 0.11 kcal mol-1 for t-BVE and Z-MPE, respectively). The HF/3-21G method, however, predicts a planar structure (φe= 180°) for t-BVE and an anticlinal structure (φe = 138.7°) for Z-MPE.

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Section: Discussionsupporting

confidence: 57%

“…A similar lengthening of O-C bonds has been observed between Me 2 O (1.415(1) Å) 29 and (t-Bu) 2 O (1.436(4) Å). 30 The CdC-O angles are larger (126-128°) in the syn structures than those in the anti forms (120-123°). Only small variations occur for the C-O-C angles.…”

Section: Methodsmentioning

confidence: 97%

Gas-Phase Structures and Conformational Properties of tert-Butyl Vinyl Ether and (Z)-Methyl 1-Propenyl Ether

Leibold

Oberhammer

1998

J. Am. Chem. Soc.

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“…The geometry of this molecule is somewhat different in MM4 and MM3, compared with the observed data. 26 The most obvious difference is the CO bond length. The OCC and CCC angles are also changed.…”

Section: Results and Discussion4bmentioning

confidence: 99%

Alcohols, ethers, carbohydrates, and related compounds. I. The MM4 force field for simple compounds

et al. 2003

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Simple alcohols and ethers have been studied with the MM4 force field. The structures of 13 molecules have been well fit using the MM4 force field. Moments of inertia have been fit with rms percentage errors as indicated: 18 moments for ethers, 0.28%; 21 moments for alcohols, 0.22%. Rotational barriers and conformational equilibria have also been examined, and the experimental and ab initio results are reproduced substantially better with MM4 than they were with MM3. Much of the improvement comes from the use of additional interaction terms in the force constant matrix, of which the torsion-bend and torsion-torsion are particularly important. Induced dipoles are included in the calculation, and dipole moments are reasonably well fit. It has been possible for the first time to fit conformational energetic data for both open chain and cyclic alcohols (e.g., propanol and cyclohexanol) with the same parameter set. For vibrational spectra, over a total of 82 frequencies, the rms error is 27 cm(-1), as opposed to 38 cm(-1) with MM3. Both the alpha and beta bond shortening resulting from the presence of the electronegative oxygen atom in the molecule are well reproduced. The electronegativity of the oxygen is sufficient that one must also include not only the alpha and beta electronegativity effects on bond lengths, but also on angle distortions, if structures are to be well reproduced. The heats of formation of 32 alcohols and ethers were fit overall to within experimental error (weighted standard deviation error 0.26 kcal/mol).

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“…Gregerson et al 18 have calculated MTBE and its analogues at the ab initio level isolated. Electron diffraction was used to determine the gas‐phase structures of t ‐butyl methyl ether (TBME) and dibutyl ether (DTBE) by Liedle et al 19.…”

Section: Introductionmentioning

confidence: 99%

Theoretical study of adsorption of methyltert‐butyl ether on broken clay minerals surfaces

Michalkova

Johnson

Gorb

et al. 2005

Int J of Quantum Chemistry

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ABSTRACT:The interactions between methyl tert-butyl ether (MTBE) and differently defected tetrahedral and octahedral fragments of clay minerals containing Si 4ϩ , Al 3ϩ , and Mg 2ϩ central cations have been studied at the B3LYP and MP2 levels of theory in conjunction with the 6-31G(d) basis set. MTBE interacts with defect clay structures due to the formation of multiple COH . . . O and OOH . . . O hydrogen bonds. Interactions of MTBE with systems containing different types of defected mineral fragments were found to vary. Systems containing the same type of defected mineral fragment with different central cation interact almost the same way with MTBE. The formation of hydrogen bonds leads to changes in the geometrical parameters and to the polarization of MTBE. The values of the interaction energies depend on the charge of the mineral fragment. They amount to 5 kcal/mol-35 kcal/mol. MTBE interacts more preferably with octahedral fragments than with tetrahedral fragments that contain an Al 3ϩ central cation.

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Gas-phase structures of di-t-butyl ether and t-butyl methyl ether

Cited by 24 publications

References 28 publications

Gas-Phase Structures and Conformational Properties of tert-Butyl Vinyl Ether and (Z)-Methyl 1-Propenyl Ether

Gas-Phase Structures and Conformational Properties of tert-Butyl Vinyl Ether and (Z)-Methyl 1-Propenyl Ether

Alcohols, ethers, carbohydrates, and related compounds. I. The MM4 force field for simple compounds

Theoretical study of adsorption of methyltert‐butyl ether on broken clay minerals surfaces

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