Bimolecular reactions of carbenes: Proton transfer mechanism

被引：6

作者：

Abu-Saleh, Abd Al-Aziz A. ^{[1
]}

Almatarneh, Mansour H. ^{[1
,2
]}

Poirier, Raymond A. ^{[1
]}

机构：

[1] Mem Univ Newfoundland, Dept Chem, St John, NF A1B 3X7, Canada

[2] Univ Jordan, Dept Chem, Amman 11942, Jordan

来源：

CHEMICAL PHYSICS LETTERS | 2018年 / 698卷

基金：

加拿大自然科学与工程研究理事会;

关键词：

DEAMINATION REACTION; STABLE CARBENES; AB-INITIO; TRIPLET CARBENE; CARBON; DECOMPOSITION; WATER; ACTIVATION; ETHYLAMINE; CYTOSINE;

D O I：

10.1016/j.cplett.2018.03.001

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

Here we report the bimolecular reaction of trifluoromethylhydroxycarbene conformers and the water-mediated mechanism of the 1,2-proton shift for the unimolecular trans-conformer by using quantum chemical calculations. The CCSD(T)/cc-pVTZ//MP2/cc-pVDZ potential-energy profile of the bimolecular reaction of cis- and trans-trifluoromethylhydroxycarbene, shows the lowest gas-phase barrier height of 13 kJ mol(-1) compared to the recently reported value of 128 kJ mol(-1) for the unimolecular reaction. We expect bimolecular reactions of carbene's stereoisomers will open a valuable field for new and useful synthetic strategies. (C) 2018 Elsevier B.V. All rights reserved.

引用

页码：36 / 40

页数：5

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