Effects of protonation on acetone: nuclear magnetic resonance and ab initio studies

Krivdin, Leonid B.; Зинченко, С. В.; Калабин, Г. А.; Facelli, Julio C.; Tufró, M. F.; Contreras, Rubén H.; Denisov, A. Yu.; Gavrilyuk, Oksana A.; Mamatyuk, V. I.

doi:10.1039/ft9928802459

Cited by 36 publications

(16 citation statements)

References 28 publications

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“…Calculated gas-phase structures of acetone, protonated acetone, and a hydrogen-bonded acetone dimer are reported in Figure . The internal coordinates for acetone in Figure are consistent with those in earlier work and in a recent report for acetone optimized at MP2/tzp; and a frequency analysis shows that the minimum-energy geometry has C 2 symmetry. The calculated proton affinity of acetone at MP2/6-311+G* is 185.4 kcal/mol.…”

Section: Theoretical Resultssupporting

confidence: 88%

Theoretical and Experimental Study of the ¹³C Chemical Shift Tensors of Acetone Complexed with Brønsted and Lewis Acids

Barich

Nicholas

et al. 1998

J. Am. Chem. Soc.

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We calculated the chemical shift tensors for acetone and 12 complexes of acetone with Brønsted and Lewis acids. Each complex was optimized at the MP2/6-311+G* or B3LYP/DZVP2 level of theory. Chemical shift tensors were calculated with the gauge including atomic orbital (GIAO) approach at the RHF and MP2 levels of theory. We discovered a strong correlation between the MP2 and RHF 13C isotropic shifts of the carbonyl carbon in the complexes studied. Linear regression indicates that the MP2 isotropic shifts can be predicted by δMP2 = [1.12 (±0.04)]δRHF − 42.1 (±10.5) ppm (R 2 = 0.9974). We were thus able to study two systems that are currently intractable at the GIAO-MP2 level. One is the complex of acetone with a large model of a zeolite, (H3SiO)3SiOHAl(OSiH3)3. The RHF shift of the carbonyl carbon of acetone on the zeolite model (238.4 ppm) is in poor agreement with the experimental (223 ppm) value. However, the MP2 result predicted by the linear correlation (224.0 ppm) is in much closer agreement. We were also able to study acetone adsorbed on aluminum chloride powder models. We find that acetone·AlCl3 is a poor adsorption model, as demonstrated by a large discrepancy between experimental and calculated MP2 shifts. However, the MP2 shift from the regression equation (244.7 ppm) for acetone complexed to the larger Al2Cl6 cluster is in excellent agreement with the experimental result (245 ppm). We also report experimental measurements of the principal components of the carbonyl 13C shift tensor for a variety of solid acids, including frozen oleum and frozen SbF5.

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Section: Theoretical Resultssupporting

confidence: 88%

Theoretical and Experimental Study of the ¹³C Chemical Shift Tensors of Acetone Complexed with Brønsted and Lewis Acids

Barich

Nicholas

et al. 1998

J. Am. Chem. Soc.

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“…The first observation of the lone pair effect on 1 J(C,C) coupling constants was report for a series of oximes including the title compound ethanaloxime [69]. Previous semi-empirical [85,86] and DFT [79] calculations on acetoxime as well as DFT [78] and SOPPA(CCSD) [16] calculations on methanimine showed that only the FC contribution is changed by the lone pair effect. Furthermore an analysis of the contributions of individual localized DFT molecular orbitals to the FC term in the same molecules [78,79] indicated that this effect is primarily due to a direct lone pair contribution from the corresponding localized orbital, which is positive for the coupling synperiplanar to the lone pair and negative for the coupling antiperiplanar to it.…”

Section: One-bond Couplingmentioning

confidence: 99%

The Effect of Substituents on Indirect Nuclear Spin-Spin Coupling Constants: Methan- and Ethanimine, Methanal- and Ethanaloxime

Provasi

Aucar

Sauer

2003

IJMS

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Ab initio calculations of the spin-spin coupling constants have been carried out for methan-and ethanimine, methanal-and ethanaloxime at the level of the second order polarization propagator approximation with coupled cluster singles and doubles amplitudes (SOPPA(CCSD)) using the aug-cc-pVTZ-J basis sets. Previously we have shown that this method can reproduce quantitatively the coupling constants for methanimine; our new results for methanal-and ethanaloxime agree also very well with the measured couplings. A study of both purely geometrical and substituent effects on all coupling constants in the title compounds is presented. Analyzing the four contributions to the coupling constants we find that the stereoelectronic effect of the nitrogen lone pair on the one-bond C-H and C-C couplings as well as the corresponding effect for the geminal N-H and N-C couplings is affected strongly by the -OH substituent. For the one-bond C-N couplings we observe that the orbital paramagnetic (OP) contribution is comparable to the Fermi Contact (FC) contribution but opposite in sign and that the spin-dipolar (SD) term amounts to between 40% and 85% of the total coupling constants. Changes in the total one-bond C-N couplings caused by the -OH substituent are also almost entirely due to SD contribution.

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“…We start this section with the discussion of the so-called "lone pair effect", originally reviewed by Gil and von Philipsborn. [231] The Lone Pair Effect (LPE) was reported for carbon-carbon coupling constants as early as in 1984, [232] which further received its theoretical explanation in the papers by Contreras, et al [233][234][235][236][237] The application of LPE opened a new guide for the stereochemical assignment of imines and related molecules. [238][239][240][241][242][243] In a continuation of those studies, this effect was also documented and theoretically interpreted for carbonhydrogen coupling constants (Scheme 9) which is discussed in more detail below.…”

Section: Functional Derivativesmentioning

confidence: 99%

Computational¹H and¹³C NMR in structural and stereochemical studies

Krivdin

2022

Magnetic Reson in Chemistry

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Present review outlines the advances and perspectives of computational 1H and 13C NMR applied to the stereochemical studies of inorganic, organic, and bioorganic compounds, involving in particular natural products, carbohydrates, and carbonium ions. The first part of the review briefly outlines theoretical background of the modern computational methods applied to the calculation of chemical shifts and spin–spin coupling constants at the DFT and the non‐empirical levels. The second part of the review deals with the achievements of the computational 1H and 13C NMR in the stereochemical investigation of a variety of inorganic, organic, and bioorganic compounds, providing in an abridged form the material partly discussed by the author in a series of parent reviews. Major attention is focused herewith on the publications of the recent years, which were not reviewed elsewhere.

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Effects of protonation on acetone: nuclear magnetic resonance and ab initio studies

Cited by 36 publications

References 28 publications

Theoretical and Experimental Study of the ¹³C Chemical Shift Tensors of Acetone Complexed with Brønsted and Lewis Acids

Theoretical and Experimental Study of the ¹³C Chemical Shift Tensors of Acetone Complexed with Brønsted and Lewis Acids

The Effect of Substituents on Indirect Nuclear Spin-Spin Coupling Constants: Methan- and Ethanimine, Methanal- and Ethanaloxime

Computational¹H and¹³C NMR in structural and stereochemical studies

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Effects of protonation on acetone: nuclear magnetic resonance and ab initio studies

Cited by 36 publications

References 28 publications

Theoretical and Experimental Study of the 13C Chemical Shift Tensors of Acetone Complexed with Brønsted and Lewis Acids

Theoretical and Experimental Study of the 13C Chemical Shift Tensors of Acetone Complexed with Brønsted and Lewis Acids

The Effect of Substituents on Indirect Nuclear Spin-Spin Coupling Constants: Methan- and Ethanimine, Methanal- and Ethanaloxime

Computational1H and13C NMR in structural and stereochemical studies

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Product

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Theoretical and Experimental Study of the ¹³C Chemical Shift Tensors of Acetone Complexed with Brønsted and Lewis Acids

Theoretical and Experimental Study of the ¹³C Chemical Shift Tensors of Acetone Complexed with Brønsted and Lewis Acids

Computational¹H and¹³C NMR in structural and stereochemical studies