Transition Metal-like Oxidative Addition of C-F and C-O Bonds to an Aluminum(I) Center

被引：108

作者：

Chu, Terry ^{[1
]}

Boyko, Yaroslav ^{[1
]}

Korobkov, Ilia ^{[2
]}

Nikonov, Georgii I. ^{[1
]}

机构：

[1] Brock Univ, Dept Chem, St Catharines, ON L2S 3A1, Canada

[2] Univ Ottawa, Fac Sci, Xray Core Facil, Ottawa, ON K1N 6N5, Canada

来源：

ORGANOMETALLICS | 2015年 / 34卷 / 22期

关键词：

ACTIVATION; FLUORINE; HYDRODEFLUORINATION; CLEAVAGE; IRIDIUM; DIHYDROGEN; HYDROGEN; COMPLEX; AMMONIA;

D O I：

10.1021/acs.organomet.5b00793

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Oxidative addition of very robust C-F and C-O bonds has been accomplished in reactions of the aluminum(I) compound NacNacAl (1, NacNac = [ArNC-(Me)CHC(Me)NA](-) and Ar = 2,6-(Pr2C6H3)-C-1) with fluoroarenes, fluoroalkanes, and ethers. Similar to the transition metals, the ease of aryl C-F oxidative addition decreases as the degree of fluorination diminishes on the aromatic substrate. As well, kinetic studies on the addition of 1,2,3,4-tetrafluorobenzene to compound 1 revealed a second-order reaction characterized by a very negative entropy of activation (Delta S = -113.6(3) J/K.mol), consistent with a transition metal-like oxidative addition process.

引用

页码：5363 / 5365

页数：3

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