Kinetic isotope effects on thio-substituted biological phosphoryl transfer reactions from density-functional theory

2005 ◽  
pp. 3909 ◽  
Author(s):  
Yun Liu ◽  
Xabier Lopez ◽  
Darrin M. York
Keyword(s):  
Density Functional Theory ◽  
Density Functional ◽  
Isotope Effects ◽  
Kinetic Isotope Effects ◽  
Transfer Reactions ◽  
Phosphoryl Transfer ◽  
Functional Theory ◽  
Kinetic Isotope

scholarly journals Density functional theory study of thermodynamic and kinetic isotope effects of H2/D2 dissociative adsorption on transition metals

2018 ◽  
Vol 8 (13) ◽  
pp. 3321-3335 ◽  
Author(s):  
Yunhai Bai ◽  
Benjamin W. J. Chen ◽  
Guowen Peng ◽  
Manos Mavrikakis
Keyword(s):  
Density Functional Theory ◽  
Transition Metals ◽  
Active Sites ◽  
Density Functional ◽  
Isotope Effects ◽  
Kinetic Isotope Effects ◽  
Dissociative Adsorption ◽  
Density Functional Theory Study ◽  
Functional Theory ◽  
Kinetic Isotope

Thermodynamic/kinetic isotope effects for H2/D2 dissociative adsorption calculated on metal surfaces offer a means to identify active sites.

A Combined Computational–Experimental Study of the Kinetics of Intramolecular Diels–Alder Reactions in a Series of 1,3,8-Nonatrienes

2015 ◽  
Vol 68 (2) ◽  
pp. 230 ◽  
Author(s):  
William J. Lording ◽  
Alan D. Payne ◽  
Tory N. Cayzer ◽  
Michael S. Sherburn ◽  
Michael N. Paddon-Row
Keyword(s):  
Density Functional ◽  
Isotope Effects ◽  
Activation Parameters ◽  
Kinetic Isotope Effects ◽  
Alder Reaction ◽  
Diels Alder ◽  
Functional Theory ◽  
Kinetic Isotope ◽  
Diels Alder Reaction ◽  
Kinetics Of

Activation enthalpies for a series of five 1,3,8-nonatriene intramolecular Diels–Alder (IMDA) reactions involving substrates 1–5 have been determined experimentally and Singleton’s natural abundance method has been employed to determine kinetic isotope effects in the IMDA reaction of fumarate 3. The activation enthalpies for the IMDA reactions of the systems possessing a –CH2OCH2– diene/dienophile tether are significantly smaller than their counterparts possessing the –CH2OC(=O)– tether. The experimental activation enthalpies have been used to benchmark computed values from four model chemistries, namely two density functional theory functionals, B3LYP and M06-2X, and two generally very accurate composite ab initio wave function methods, CBS-QB3 and G4(MP2). G4(MP2) outperformed the computationally more expensive CBS-QB3 method, but the vastly cheaper M06-2X/6-31G(d)//B3LYP/6-31G(d) method was sufficiently accurate to be the recommended method of choice for calculating activation parameters. Experimental 2H kinetic isotope effects for the IMDA reaction of fumarate 3 confirmed the computational predictions that this Diels–Alder reaction is concerted but asynchronous.

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