Mechanism of the Catalytic Carboxylation of Alkylboronates with CO2 Using Ni-NHC Complexes: A DFT Study

被引：12

作者：

Delarmelina, Maicon ^{[1
]}

Marelli, Enrico ^{[2
]}

Carneiro, Jose Walkimar de M. ^{[1
]}

Nolan, Steven P. ^{[3
,4
]}

Buhl, Michael ^{[2
]}

机构：

[1] Univ Fed Fluminense, Inst Quim, BR-24020141 Niteroi, RJ, Brazil

[2] Univ St Andrews, Sch Chem, St Andrews KY16 9ST, Fife, Scotland

[3] Univ Ghent, Dept Chem, Campus Sterre,Bldg S-3,Krijgslaan 281, B-9000 Ghent, Belgium

[4] Univ Ghent, Ctr Sustainable Chem, Campus Sterre,Bldg S-3,Krijgslaan 281, B-9000 Ghent, Belgium

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2017年 / 23卷 / 59期

基金：

英国工程与自然科学研究理事会;

关键词：

carbon dioxide; carboxylation; density functional calculations; N-heterocyclic carbenes; nickel; C-H BONDS; CARBON-DIOXIDE; APPROXIMATION; ESTERS; ENERGY; MODEL; BENCHMARKING;

D O I：

10.1002/chem.201703567

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

A new mechanism is proposed for the Ni-catalyzed carboxylation of organoboronates with CO2. DFT investigations at the PBE0-D3 level have shown that direct CO2 addition to the catalysts [Ni(NHC)(Allyl)Cl] (1(NHC), NHC=IMe, IPr, SIPr and IPr*) is kinetically disfavored and formation of the Aresta-type intermediate is unlikely to occur. According to the mechanism proposed here, the carboxylation process starts with addition of the borate species to 1(NHC), followed by transmetalation, CO2 cycloaddition and carboxylation. The rate-determining step was identified as being the transmetalation process, with computed relative free energy barriers of 34.8, 36.8, and 33.5 kcal mol(-1) for 1(IPr), 1(SIPr) and 1(IPr*), respectively.

引用

页码：14954 / 14961

页数：8

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