The Difluoromethylated Organogold(III) Complex cis-[Au(PCy3)(4-F-C6H4)(CF2H)(CI)]: Preparation, Characterization, and Its C(sp2)-CF2H Reductive Elimination

被引：20

作者：

Liu, Shuanshuan ^{[1
]}

Kang, Kai ^{[2
]}

Liu, Shihan ^{[3
]}

Wang, Decai ^{[1
]}

Wei, Ping ^{[1
]}

Lan, Yu ^{[3
,4
]}

Shen, Qilong ^{[2
]}

机构：

[1] Nanjing Tech Univ, Biotechnol & Pharmaceut Engn, Nanjing 210009, Jiangsu, Peoples R China

[2] Chinese Acad Sci, Univ Chinese Acad Sci, Shanghai Inst Organ Chem, Key Lab Organofluorine Chem,Ctr Excellence Mol Sy, 345 Lingling Rd, Shanghai 200032, Peoples R China

[3] Chongqing Univ, Sch Chem & Chem Engn, Chongqing 400030, Peoples R China

[4] Zhengzhou Univ, Coll Chem & Mol Engn, Zhengzhou 450001, Henan, Peoples R China

来源：

ORGANOMETALLICS | 2018年 / 37卷 / 21期

基金：

中国国家自然科学基金;

关键词：

PALLADIUM-CATALYZED DIFLUOROMETHYLATION; OXIDATIVE ADDITION; ORGANIC-SYNTHESIS; GOLD COMPLEXES; BOND-FORMATION; C-H; FLUORINE; PD; TRIFLUOROMETHYLATION; REACTIVITY;

D O I：

10.1021/acs.organomet.8b00579

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The preparation of the difluoromethylated organogold(III) complex cis-[Au(PCy3)(4-F-C6H4)(CF2H)(Cl)] (3) and its Ar-CF2H reductive elimination are described. In the presence of 1.0 equiv of AgSbF6 or AgPF6, compound 3 underwent a quantitative Ar-CF2H reductive elimination in less than 1.0 min at 25 degrees C, while the lack of silver salt resulted in Ar-CF2H reductive elimination from complex 3 in 1,1,2,2-tetrachloroethane (CCl2HCCl2H) after 80 min at 115 degrees C to afford the elimination product p-F-PhCF2H (4) and (Cy3P)Au(Cl) in quantitative yields. On the basis of the mechanistic studies of the kinetics of the reaction and DFT calculation, a concerted Ar-CF2H bond-forming pathway for the Ar-CF2H reductive elimination from organogold(III) complex 3 is proposed.

引用

页码：3901 / 3908

页数：8

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