Über die Existenz des Oxoniumperchlorats

Volmer, M.

doi:10.1002/jlac.19244400119

Cited by 67 publications

(14 citation statements)

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“…than that in [H3 O + ][HSO 4 -] (SAM) measured at 77 K, ) 7.513 MHz 17. The different17 O QCC values may be attributed to the different HB strengths of the two compounds.…”

mentioning

confidence: 63%

A Solid-State NMR and Theoretical Study of the ¹⁷O Electric Field Gradient and Chemical Shielding Tensors of the Oxonium Ion in p-Toluenesulfonic Acid Monohydrate

Hook

Dong

et al. 2000

J. Phys. Chem. A

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We report a solid-state 17 O NMR study of the 17 O electric field gradient (EFG) and chemical shielding (CS) tensors for the oxonium ion, H 3 O + , in p-toluenesulfonic acid monohydrate (TAM). Both the 17 O EFG and CS tensors of the H 3 O + ion are axially symmetric within the experimental errors. The 17 O quadrupole coupling constant (QCC) is found to be 7.05 ( 0.02 MHz, and the 17 O chemical shift anisotropy (CSA) is 87 ( 5 ppm. Experimental results are compared with extensive quantum chemical calculations using restricted HartreeFock approach (RHF), second-order Møller-Plesset perturbation theory (MP2), and density functional theory (DFT). The calculations showed that the strong hydrogen-bonding environment around the H 3 O + ion in TAM is responsible for a reduction of approximately 3 MHz in the 17 O QCC compared to that of an isolated H 3 O + ion. The effective 17 O quadrupole moment is calibrated at the B3LYP/cc-pVTZ level, Q ) -2.400 fm 2 . Using this value, we obtained the best calculated 17 O QCC for the "bound" H 3 O + ion, +7.382 MHz, which is in reasonably good agreement with the observed value. The 17 O chemical shielding tensor is also calculated using the GIAO (gauge-including atomic orbital) approach. Although the calculated isotropic 17 O chemical shifts are in excellent agreement with the experimental data, the calculations with all the basis sets employed in the present study invariably underestimated 17 O CSAs by approximately 20 ppm.

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“…than that in [H3 O + ][HSO 4 -] (SAM) measured at 77 K, ) 7.513 MHz 17. The different17 O QCC values may be attributed to the different HB strengths of the two compounds.…”

mentioning

confidence: 63%

A Solid-State NMR and Theoretical Study of the ¹⁷O Electric Field Gradient and Chemical Shielding Tensors of the Oxonium Ion in p-Toluenesulfonic Acid Monohydrate

Hook

Dong

et al. 2000

J. Phys. Chem. A

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“…The H 3 O + ion has been known since the early 1920s 1 and has been studied in crystalline acid monohydrates by vibrational spectroscopy (IR and Raman), [2][3][4][5][6][7] and by X-ray [3][4][5][6][7][8][9][10][11] and neu-tron 12,13 diffraction methods. Studies of H 3 O + and its solvates in the gas phase continue to draw interest, [14][15][16] as do calculational approaches.…”

Section: Introductionmentioning

confidence: 99%

The Nature of the H₃O⁺ Hydronium Ion in Benzene and Chlorinated Hydrocarbon Solvents. Conditions of Existence and Reinterpretation of Infrared Data

2006

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Salts of the C3v symmetric hydronium ion, H3O + , have been obtained in the weakly basic solvents benzene, dichloromethane, and 1,2-dichloroethane. This is made possible by using carborane counterions of the type CHB 11R5X6-(R) H, Me, Cl; X) Cl, Br, I) because they combine the three required properties of a suitable counterion: very low basicity, low polarizability, and high chemical stability. The existence of the H 3O + ion requires the formation of three more-or-less equivalent, medium-to-strong H-bonds with solvent or anion bases. With the least basic anions such as CHB11Cl11-, IR spectroscopy indicates that C3v symmetric trisolvates of formulation [H3O + ‚3Solv] are formed with chlorocarbon solvents and benzene, the latter with the formation of π bonds. When the solvents and anions have comparable basicity, contact ion pairs of the type [H3O + ‚nSolv‚Carborane] are formed and close to C3v symmetry is retained. The conditions for the existence of the H3O + ion are much more exacting than previously appreciated. Outside of the range of solvent basicity bounded at the lower end by dichloromethane and the upper end by tributyl phosphate, and with anions that do not meet the stringent requirements of weak basicity, low polarizability of high chemical stability, lower symmetry species are formed. One H-bond from H 3O + to the surrounding bases becomes stronger than the other two. The distortion from C3v symmetry is minor for bases weaker than dichloromethane. For bases stronger than tributyl phosphate, H2O-H +-B type species are formed that are more closely related to the H5O2 + ion than to H3O +. IR data allow criteria to be defined for the existence of the symmetric H3O + ion. This includes a linear dependence between the frequencies of νmax(OH) and δ(OH3) within the ranges 3010-2536 cm-1 for νmax(OH) and 1597-1710 cm-1 for δ(OH3). This provides a simple way to assess the correctness of the formulation of the proton state in monohydrated acids. In particular, the 30-year-old citation classic of the IR spectrum believed to arise from H 3O + SbCl6is reinterpreted in terms of (H2O)x‚HSbCl6 hydrates. The correctness of the hydronium ion formulation in crystalline H3O + Asalts (A-) Cl-, NO3-) is confirmed, although, when Ais a fluoroanion, distortions from C3v symmetry are suggested.

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“…la). For this case, the second-order rate constant in AT-1 sec.-1 was found to be given by 2wN 000 RiJOnf (1) where N is Avogadro's number, Rv2 is the reaction radius, Du is the sum of the diffusion coefficients of enzyme and substrate, and / is a factor taking into account electrostatic interactions which is given by 1 r J R12 evm 1 dr (2) In this equation, V is the electrical potential energy which is a function of r. The electrostatic factor was calculated at infinite dilution and in the limiting law region assuming that the effect of the net protein charge is negligible compared with that of the net charge of the active site. The potential energy used for these cases was4…”

Section: Introductionmentioning

confidence: 99%

The Influence of the Net Protein Charge on the Rate of Formation of Enzyme–Substrate Complexes.

Hammes¹,

Alberty²

1959

J. Phys. Chem.

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Über die Existenz des Oxoniumperchlorats

Cited by 67 publications

References 0 publications

A Solid-State NMR and Theoretical Study of the ¹⁷O Electric Field Gradient and Chemical Shielding Tensors of the Oxonium Ion in p-Toluenesulfonic Acid Monohydrate

A Solid-State NMR and Theoretical Study of the ¹⁷O Electric Field Gradient and Chemical Shielding Tensors of the Oxonium Ion in p-Toluenesulfonic Acid Monohydrate

The Nature of the H₃O⁺ Hydronium Ion in Benzene and Chlorinated Hydrocarbon Solvents. Conditions of Existence and Reinterpretation of Infrared Data

The Influence of the Net Protein Charge on the Rate of Formation of Enzyme–Substrate Complexes.

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Über die Existenz des Oxoniumperchlorats

Cited by 67 publications

References 0 publications

A Solid-State NMR and Theoretical Study of the 17O Electric Field Gradient and Chemical Shielding Tensors of the Oxonium Ion in p-Toluenesulfonic Acid Monohydrate

A Solid-State NMR and Theoretical Study of the 17O Electric Field Gradient and Chemical Shielding Tensors of the Oxonium Ion in p-Toluenesulfonic Acid Monohydrate

The Nature of the H3O+ Hydronium Ion in Benzene and Chlorinated Hydrocarbon Solvents. Conditions of Existence and Reinterpretation of Infrared Data

The Influence of the Net Protein Charge on the Rate of Formation of Enzyme–Substrate Complexes.

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A Solid-State NMR and Theoretical Study of the ¹⁷O Electric Field Gradient and Chemical Shielding Tensors of the Oxonium Ion in p-Toluenesulfonic Acid Monohydrate

A Solid-State NMR and Theoretical Study of the ¹⁷O Electric Field Gradient and Chemical Shielding Tensors of the Oxonium Ion in p-Toluenesulfonic Acid Monohydrate

The Nature of the H₃O⁺ Hydronium Ion in Benzene and Chlorinated Hydrocarbon Solvents. Conditions of Existence and Reinterpretation of Infrared Data