Transition state

About: Transition state is a research topic. Over the lifetime, 4978 publications have been published within this topic receiving 117965 citations. The topic is also known as: transition state of elementary reaction.

Hydroxyl radical reactions with phenol as a model for generation of biologically reactive tyrosyl radicals

Abstract: Reactions of the hydroxyl radical with phenol, as model for the generation of biologically harmful tyrosyl radicals, have been investigated using high level quantum chemical techniques. Hybrid Hartree−Fock density functional theory (HF-DFT) calculations, using the B3LYP functional, and standard ab initio HF and second-order Moller−Plesset perturbation theory (MP2) calculations are employed to locate addition complexes, transition state structures, and products for OH addition to the various positions in the aromatic ring, as well as for direct abstraction of the phenolic hydrogen and for the observed water elimination from 1,2-dihydroxy-cyclohexadienyl. Although the different methods yield some variation in terms of barrier heights and addition complex geometries, a consistent picture is provided by the DFT and spin projected MP2 data. In summary the present calculations support previous experimental observations reporting essentially diffusion-controlled mechanisms for ring OH addition and direct hydroge...

Insights on co-catalyst-promoted enamine formation between dimethylamine and propanal through ab initio and density functional theory study.

Abstract: The mechanistic details on enamine formation between dimethylamine and propanal are unraveled using the ab initio and density functional theory methods. The addition of secondary amine to the electrophile and simultaneous proton transfer results in a carbinolamine intermediate, which subsequently undergoes dehydration to form enamine. The direct addition of amine as well as the dehydration of the resulting carbinolamine intermediate is predicted to possess fairly high activation barrier implying that a unimolecular process is unlikely to be responsible for enamine formation. Different models are therefore proposed which could explain the relative ease of enamine formation under neat condition as well as under the influence of methanol as the co-catalyst. The explicit inclusion of either the reagent or the co-catalyst is considered in the transition states as stabilizing agents. The participation of the reagent or the co-catalyst as a monofunctional ancillary species is found to stabilize the transition states relative to the unassisted or the direct addition/dehydration pathways. The reduction in enthalpy of activation is found to be much more dramatic when two co-catalysts participate in an active bifunctional mode in the rate-determining dehydration step. The transition structures exhibited characteristic features of a relay proton transfer mechanism. The free energy of activation associated with the two methanol-assisted pathway is found to be 16.7 kcal/mol lower than that of the unassisted pathway. The results are found to be in concurrence with the available reports on the rate acceleration by co-catalysts in the Michael reaction between enamine and methyl vinyl ketone under neat conditions.

Computational Rationalization of the Dependence of the Enantioselectivity on the Nature of the Catalyst in the Vanadium-Catalyzed Oxidation of Sulfides by Hydrogen Peroxide

Abstract: A computational study with the IMOMM(Becke3LYP:MM3) method is carried out on the mechanism of the enantioselective reaction of complex V(O)(L)(OOH), L= bulky tridentate Schiff base, and bis(tert-butyl) disulfide. The reaction with a given L ligand A is first systematically studied: different conformers of the catalyst are optimized, and the large number of associated transition states are systematically searched. The study is then extended to the geometry optimization of selected transition states associated to other ligands B, C, and D, similar to A but differing in the nature of certain substituents R1, R2, R3. The experimental trends in selectivity for catalysts based on ligands A to D are faithfully reproduced by the calculations. Analysis of the computational results leads finally to the formulation of a simple model that can explain one of the most remarkable aspect of this reaction, namely the large effect on enantioselectivity of ligands seemingly far from each other in the catalyst.

Olefin Epoxidation by Methyltrioxorhenium: A Density Functional Study on Energetics and Mechanisms.

Abstract: A spiro attack on a peroxo group is calculated to be the preferred reaction pathway for olefin epoxidation with the catalytic system CH3 ReO3 /H2 O2 (see picture). This finding is supported by density functional calculations on more than ten transition states for the most probable mechanisms. Hydration has significant effects on various reaction species: it stabilizes the intermediates and destabilizes, with one exception, the transition states.

Toward the understanding of ethylene photodissociation: Theoretical study of energy partition in products and rate constants

Abstract: The energy partition in the products of ethylene photodissociation (including C2H4, C2D4, D2CCH2, cis- and trans-HDCCDH) at 193 and 157 nm and the rate constants of H loss channels were computed based on ab initio ethylene ground-state surfaces of which most were reported earlier. In the calculations of the energy partitions, a simple model was used in which the excess energy above the transition state is distributed statistically and the energy released by the exit barrier is described by the modified impulsive model. The rate constants of the ethylene H(D) elimination were calculated according to the variational RRKM (Rice–Ramsperger–Kassel–Marcus) theory, and the RRKM rate constants with tunneling corrections were obtained for vinyl decomposition at 193 nm. In contrast with previous conclusions drawn by LIF (laser induced fluorescence) studies, the rate constant calculations suggest that the H loss may be a nonstatistical process. However, the computed variational transition states for H loss appear re...