Phenomenological manifestations of large-curvature tunneling in hydride-transfer reactions

Kreevoy, Maurice M.; Ostovic, Drazen; Truhlar, Donald G.; Garrett, Bruce C.

doi:10.1021/j100407a052

Cited by 104 publications

(120 citation statements)

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“…255 The most serious problem with using Swain-Schaad-type arguments to derive quasiclassical limits for the relationship of H/T to D/T KIEs is that such arguments are based on one-dimensional models of tunneling, but we have known for a long time that the effective potential for tunneling depends on the isotopic composition of the system. 256,257 This and other multidimensional effects on tunneling 57,[258][259][260][261] invalidate the use of one-dimensional models for reliable work. 236 …”

Section: Previous Reviewsmentioning

confidence: 99%

Multidimensional Tunneling, Recrossing, and the Transmission Coefficient for Enzymatic Reactions

2006

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Section: Previous Reviewsmentioning

confidence: 99%

Multidimensional Tunneling, Recrossing, and the Transmission Coefficient for Enzymatic Reactions

2006

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“…However, a variety of 1,4-dihydroquinolines (1 1, 13, 24, 25, 29), 9,lO-dihydroacridines (1 1, 13, 24, 25, 30, 31), and 5,6-dihydrophenanthridines (1 1, 13, 30, 32) have also been used as hydride donors in the continuing investigations of "model nicotinamide-coenzyme reactions". These reactions have also attracted interest as vehicles for the evaluation of some fundamental principles of physical organic chemistry (11,13,31,32).…”

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confidence: 99%

Kinetics of hydride transfer between nitrogen heteroaromatic cations

Bunting¹,

Luscher²

1988

Can. J. Chem.

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. 66,2524 (1988).The kinetics of the reduction of the 3-cyano-1-methylquinolinium, 4-cyano-2-methylisoquinolinium, and 2-methyl-5-nitroisoquinolinium cations by 9,lO-dihydro-10-methylacridine, and also the reduction of these same three cations as well as the 10-methylacridinium cation by 5,6-dihydro-5-methylphenanthridine, have been investigated in 20% acetonitrile -80% water, ionic strength 1.0, 25°C. The reactions of the 2-methyl-5-nitroisoquinolinium cation with both reductants, and also of the 4-cyano-2-methylisoquinolinium cation with 9,lO-dihydro-10-methylacridine, display kinetic saturation effects in the pseudo-first-order rate constants as a function of heterocyclic cation concentration. These effects are consistent with the formation of 1: 1 association complexes between hydride donor and acceptor prior to the rate-determining step of the reduction. The second-order rate constants for these reactions, and also those for analogous heterocyclic catibn reductions by 1,4-dihydronicotinamides, show systematic variations as a function of the hydride donor and acceptor species. JOHN W. BUNTING et MARK A. LUSCHER. Can. J. Chem. 66,2524Chem. 66, (1988 OpCrant A 25"C, ti une force ionique de 1,0, dans une solution d'acktonitrile dans l'eau 20:80, on a CtudiC la cinCtique de la reduction des cations cyano-3 mtthyl-1 quinolinium, cyan04 mCthyl-2 isoquinolinium et methyl-2 nitro-5 isoquinolinium par la dihydro-9,10 methyl-10 acridine ainsi que la reduction de ces trois mCme cations ainsi que celle du cation methyl-10 acridinium par la dihydro-5,6 mkthyl-5 phenanthridine. Les reactions du cation methyl-2 nitro-5 isoquinolinium avec chacun des reactifs ainsi que celle du cation cyano-4 methyl-2 isoquinolinium avec la dihydro-9,10 mtthyl-10 acridine presentent des effets de saturation cinCtique des constantes de vitesse du pseudo premier ordre en fonction de la concentration de cation hCtCrocyclique. Ces effets sont en accord avec la formation de complexes d'association 1: 1 entre le donneur et l'accepteur d'hydrure avant 1'Ctape qui determine la vitesse de la reduction. Les constantes de vitesse du deuxibme ordre de ces reactions, ainsi que celles des rkductions analogues de cations hCterocycliques par les dihydro-1,4 nicotinamides, presentent des variations systimatiques en fonction des espkces qui donne ou qui accepte l'hydrure.[Traduit par la revue]

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“…31,32 The effects of tunneling are then incorporated into the final rate constant by multiplying the quasiclassical MS-CVT rate constant (i.e., the rate constant evaluated by accounting for quantum mechanical effects in vibrational modes transverse to the reaction coordinate but with motion along the reaction coordinate itself assumed to be classical) by the ground-state transmission coefficient κ SCT . 31,32 The effect of nonclassical reflection on the rate constant is also included in κ SCT . An underlying assumption in the SCT model is that the ground-state vibrationally adiabatic potential curve, V a G , is a fairly reasonable representation of the shapes of the excited-state vibrationally adiabatic potential curves, 33,34 consequently, all of the tunneling probabilities are evaluated using the V a G as the sole effective potential in the SCT approximation.…”

Section: Ms-lhmentioning

confidence: 99%

Computational Study of the Thermochemistry of N₂O₅ and the Kinetics of the Reaction N₂O₅ + H₂O → 2 HNO₃

Alecu

Marshall

2014

J. Phys. Chem. A

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The multistructural method for torsional anharmonicity (MS-T) is employed to compute anharmonic conformationally averaged partition functions which then serve as the basis for the calculation of thermochemical parameters for N 2 O 5 over the temperature range 0−3000 K, and thermal rate constants for the hydrolysis reaction N 2 O 5 + H 2 O → 2 HNO 3 over the temperature range 180−1800 K. The M06-2X hybrid meta-GGA density functional paired with the MG3S basis set is used to compute the properties of all stationary points and the energies, gradients, and Hessians of nonstationary points along the reaction path, with further energy refinement at stationary points obtained via single-point CCSD(T)-F12a/cc-pVTZ-F12 calculations including corrections for core−valence and scalar relativistic effects. The internal rotations in dinitrogen pentoxide are found to generate three structures (conformations) whose contributions are included in the partition function via the MS-T formalism, leading to a computed value for

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Phenomenological manifestations of large-curvature tunneling in hydride-transfer reactions

Cited by 104 publications

References 3 publications

Multidimensional Tunneling, Recrossing, and the Transmission Coefficient for Enzymatic Reactions

Multidimensional Tunneling, Recrossing, and the Transmission Coefficient for Enzymatic Reactions

Kinetics of hydride transfer between nitrogen heteroaromatic cations

Computational Study of the Thermochemistry of N₂O₅ and the Kinetics of the Reaction N₂O₅ + H₂O → 2 HNO₃

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Phenomenological manifestations of large-curvature tunneling in hydride-transfer reactions

Cited by 104 publications

References 3 publications

Multidimensional Tunneling, Recrossing, and the Transmission Coefficient for Enzymatic Reactions

Multidimensional Tunneling, Recrossing, and the Transmission Coefficient for Enzymatic Reactions

Kinetics of hydride transfer between nitrogen heteroaromatic cations

Computational Study of the Thermochemistry of N2O5 and the Kinetics of the Reaction N2O5 + H2O → 2 HNO3

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Computational Study of the Thermochemistry of N₂O₅ and the Kinetics of the Reaction N₂O₅ + H₂O → 2 HNO₃