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Electronic aspects of the hydride transfer mechanism. Ab initio analytical gradient studies of the cyclopropenyl-cation/lithium hydride model reactant system (1985)

Tapia, O. ; Andres, J. ; Aullo, J. M. ; [et al.]

College Park, Md. : American Institute of Physics (AIP)

The Journal of Chemical Physics 83 (1985), S. 4673-4682

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ISSN: 1089-7690

Source: AIP Digital Archive

Topics: Physics , Chemistry and Pharmacology

Notes: The electronic mechanisms of a model hydride transfer reaction are theoretically studied with ab inito RHF and UHF SCF MO procedures at the 4-31G basis set level and analytical gradient methods. The model system describes the reduction of cyclopropenyl cation to cyclopropene by the oxidation of lithium hydride to lithium cation. The molecular fragments corresponding to the asymptotic reactive channels characterizing the stepwise mechanisms currently discussed in the literature have been characterized. The binding energy between the fragments is estimated within a simple electrostatic approximate scheme. The results show that a hydride-ion mechanism is a likely pathway for this particular system. The system is thereafter thoroughly studied from the supermolecule approach. Reaction paths for the ground and first triplet electronic states have been calculated. The hypersurface is explored from a geometrical disposition of the reactants that mimics the one found in several dehydrogenases (perpendicular configuration). A hydride ion is found to be the particle transferred on the unconstrained as well as the constrained reaction pathways in the ground electronic state. In the triplet state (perpendicular configuration) the mechanism is stepwise: electron transfer followed by a hydrogen atom transfer. It has been noticed that the perpendicular geometrical disposition of the reactants plays an important role by polarizing the susceptible cyclopropene C–H bond in the sense of increasing the electronic density at the hydrogen nucleus. This provides a clue to rationalize several dehydrogenase's active site structure and mechanism. The reactant molecular complex found in the inverted potential energy curves, namely the LiH---Cp+ association has an electronic distribution which can be described as a hydride ion cementing two electron deficient centers corresponding to the cyclopropenyl and the lithium cations. Direct CI calculations confirm the overall picture obtained above.

Type of Medium: Electronic Resource

URL: http://dx.doi.org/10.1063/1.449039

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Quantum chemical structure-activity relationships on β-carbolines as natural monoamine oxidase inhibitors (1983)

Martin, M. ; Sanz, F. ; Campillo, M. ; [et al.]

New York, NY : Wiley-Blackwell

International Journal of Quantum Chemistry 23 (1983), S. 1643-1652

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ISSN: 0020-7608

Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics

Source: Wiley InterScience Backfile Collection 1832-2000

Topics: Chemistry and Pharmacology

Notes: The electron density and the molecular electrostatic potential of the β-carbolines are studied using ab initio STO-3G wave functions. The analysis was done from the point of view of a previous model built with monoamine oxidase substrates and irreversible inhibitors. The results confirm the usefulness of the model and make it possible to propose new precision to the molecular electrostatic potential patterns needed to have monoamine oxidase inhibitory activity.

Additional Material: 11 Ill.