Conformer-specific [1,2]H-tunnelling in captodatively-stabilized cyanohydroxycarbene (NC–C̈–OH)

André K. Eckhardt; Frederik R. Erb; Peter R. Schreiner

doi:10.1039/c8sc03720e

Conformer-specific [1,2]H-tunnelling in captodatively-stabilized cyanohydroxycarbene (NC–C̈–OH)

Chemical Science ◽

10.1039/c8sc03720e ◽

2019 ◽

Vol 10 (3) ◽

pp. 802-808 ◽

Cited By ~ 3

Author(s):

André K. Eckhardt ◽

Frederik R. Erb ◽

Peter R. Schreiner

Keyword(s):

Reaction Barrier

Trans-Cyanohydroxycarbene undergoes conformer-specific [1,2]H-tunnelling to cyanoformaldehyde through the highest penetrated reaction barrier of 33.3 kcal mol−1reported to date.

Promotion of boron diffusion and gettering by employing thin Al2O3 layer as a reaction barrier

Journal of Materials Science Materials in Electronics ◽

10.1007/s10854-020-05124-6 ◽

2021 ◽

Vol 32 (7) ◽

pp. 8205-8212

Author(s):

Zhen Zhang ◽

Ning Yang ◽

Minglei Lu ◽

Xiao Yuan ◽

Xiaojun Ye ◽

...

Keyword(s):

Boron Diffusion ◽

Al2o3 Layer ◽

Reaction Barrier

How is transition state looseness related to the reaction barrier?

Journal of the American Chemical Society ◽

10.1021/ja00212a021 ◽

1988 ◽

Vol 110 (4) ◽

pp. 1127-1131 ◽

Cited By ~ 9

Author(s):

Sason S. Shaik

Keyword(s):

Transition State ◽

Reaction Barrier

Evaluation of reaction barrier compensating coatings on SCS-6 fibers in Ti-24Al-11Nb(at%) composites

Composites Engineering ◽

10.1016/0961-9526(95)00046-p ◽

1995 ◽

Vol 5 (7) ◽

pp. 951-974 ◽

Cited By ~ 2

Author(s):

Thomas D. McGarry ◽

Marek-Jerzy Pindera ◽

Franklin E. Wawner

Keyword(s):

Reaction Barrier

The DBH24/08 Database and Its Use to Assess Electronic Structure Model Chemistries for Chemical Reaction Barrier Heights

Journal of Chemical Theory and Computation ◽

10.1021/ct800568m ◽

2009 ◽

Vol 5 (4) ◽

pp. 808-821 ◽

Cited By ~ 360

Author(s):

Jingjing Zheng ◽

Yan Zhao ◽

Donald G. Truhlar

Keyword(s):

Electronic Structure ◽

Chemical Reaction ◽

Structure Model ◽

Reaction Barrier ◽

Barrier Heights

Determination of silicon point defect parameters and reaction barrier energies from gold diffusion experiments

Journal of Applied Physics ◽

10.1063/1.358937 ◽

1995 ◽

Vol 77 (3) ◽

pp. 1320-1322 ◽

Cited By ~ 18

Author(s):

K. Ghaderi ◽

G. Hobler ◽

M. Budil ◽

L. Mader ◽

H. J. Schulze

Keyword(s):

Point Defect ◽

Reaction Barrier ◽

Gold Diffusion

DENSITY FUNCTIONAL THEORY STUDY ON THE MECHANISM OF TRIMETHYLAMINE-CATALYZED BAYLIS–HILLMAN REACTION

Journal of Theoretical and Computational Chemistry ◽

10.1142/s0219633610005554 ◽

2010 ◽

Vol 09 (supp01) ◽

pp. 65-75 ◽

Cited By ~ 10

Author(s):

JING LI ◽

WAN-YI JIANG

Keyword(s):

Density Functional Theory ◽

Density Functional ◽

Dft Method ◽

Polarizable Continuum Model ◽

Functional Theory ◽

Reaction Barrier ◽

Hydrogen Shift ◽

Rate Determining Step ◽

The Density Functional Theory ◽

Polarizable Continuum

The trimethylamine-catalyzed Baylis–Hillman reaction of formaldehyde and vinylaldehyde has been studied with the density functional theory (DFT) method of B3LYP/6-31+G(d,p). In the gas phase, the reaction involves an amine–formaldehyde–vinylaldehyde trimolecular addition transition structure followed by rate-determining intramolecular 1,3-hydrogen shift. When a bulk solvent effect of water was considered with conductor-like polarizable continuum model (CPCM), the reaction was found to follow the sequence of Michael-addition of amine to vinylaldehyde (step 1), addition of formaldehyde (step 2), and 1,3-hydrogen shift (step 3), with the 1,3-hydrogen shift as rate-determining. The overall reaction barrier is significantly reduced. When a molecule of water is involved in the reaction, the 1,3-hydrogen shift is significantly promoted so that the rate-determining step becomes the C–C bond formation. The calculated overall reaction barrier is in agreement with experimental observations.

Reaction Barrier

IUPAC Standards Online ◽

10.1515/iupac.68.0152 ◽

2016 ◽

Author(s):

Keith J. Laidler

Keyword(s):

Reaction Barrier

Spin-unrestricted random-phase approximation with range separation: Benchmark on atomization energies and reaction barrier heights

The Journal of Chemical Physics ◽

10.1063/1.4918710 ◽

2015 ◽

Vol 142 (15) ◽

pp. 154123 ◽

Cited By ~ 29

Author(s):

Bastien Mussard ◽

Peter Reinhardt ◽

János G. Ángyán ◽

Julien Toulouse

Keyword(s):

Random Phase Approximation ◽

Random Phase ◽

Phase Approximation ◽

Reaction Barrier ◽

Barrier Heights

Thermal fluctuations enable rapid protein–protein associations in aqueous solution by lowering the reaction barrier

Chemical Physics Letters ◽

10.1016/j.cplett.2015.11.014 ◽

2016 ◽

Vol 643 ◽

pp. 114-118 ◽

Cited By ~ 1

Author(s):

Honami Sakaizawa ◽

Hiroshi C. Watanabe ◽

Tadaomi Furuta ◽

Minoru Sakurai

Keyword(s):

Aqueous Solution ◽

Thermal Fluctuations ◽

Reaction Barrier

ChemInform Abstract: How Is Transition State Looseness Related to the Reaction Barrier?

ChemInform ◽

10.1002/chin.198823033 ◽

1988 ◽

Vol 19 (23) ◽

Author(s):

S. S. SHAIK

Keyword(s):

Transition State ◽

Reaction Barrier