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

被引：19

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

共 50 条

[1] Preparation and NMR spectra of difluoromethylated silver(I) and silver(III) compounds. Structure of [PNP][Ag(CF2H)(4)](+)
Eujen, R
Hoge, B
Brauer, DJ
INORGANIC CHEMISTRY, 1997, 36 (14) : 3160 - 3166
[2] Preparation and NMR Spectra of Difluoromethylated Silver(I) and Silver(III) Compounds. Structure of [PNP][Ag(CF2H)4]
Eujen, R.
Hoge, B.
Brauer, D. J.
Inorganic Chemistry, 36 (14):
[3] MECHANISMS OF ETCHING AND POLYMERIZATION IN RADIOFREQUENCY DISCHARGES OF CF4-H2,CF4-C2F4,C2F6-H2,C3F8-H2
DAGOSTINO, R
CRAMAROSSA, F
COLAPRICO, V
DETTOLE, R
JOURNAL OF APPLIED PHYSICS, 1983, 54 (03) : 1284 - 1288
[4] Tris(fluorophenyl)antimony Dicarboxylates (4-FC6H4)3Sb[OC(O)R]2 (R = CH2Cl, C6F5, C6F4H-2, CF2CF3, CF2CF2CF3) and (3-FC6H4)3Sb[OC(O)C6F4H-2]2: Synthesis and Structure
V. V. Sharutin
O. K. Sharutina
A. N. Efremov
P. A. Slepukhin
Russian Journal of Inorganic Chemistry, 2020, 65 : 992 - 998
[5] Tris(fluorophenyl)antimony Dicarboxylates (4-FC6H4)3Sb[OC(O)R]2(R = CH2Cl, C6F5, C6F4H-2, CF2CF3, CF2CF2CF3) and (3-FC6H4)3Sb[OC(O)C6F4H-2]2: Synthesis and Structure
Sharutin, V. V.
Sharutina, O. K.
Efremov, A. N.
Slepukhin, P. A.
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY, 2020, 65 (07) : 992 - 998
[6] Condensation Reactions of Trifluoronitrosomethane CF3NO with Sulfanilamide H2NC6H4SO2NH2 - Preparation of CF3NNC6H4SO2NH2, CF3NNC6H4SO2NNCF3, CH3C(O)N(H)C6H4SO2NNCF3 and CF3C(O)N(H)C6H4SO2NH2
Minkwitz, R.
Jakob, J.
Winter, A.
Zeitschrift fuer Naturforschung. B, Journal of Chemical Sciences, 52 (05):
[7] Condensation reactions of trifluoronitrosomethane CF3NO with sulfanilamide H2NC6H4SO2NH2 - Preparation of CF3NNC6H4SO2NH2, CF3NNC6H4SO2NNCF3, CH3C(O)N(H)C6H4SO2NNCF3 and CF3C(O)N(H)C6H4SO2NH2
Minkwitz, R
Jakob, J
Winter, A
ZEITSCHRIFT FUR NATURFORSCHUNG SECTION B-A JOURNAL OF CHEMICAL SCIENCES, 1997, 52 (05): : 647 - 654
[8] New or improved syntheses of the polyfluoroalcohols HOC(cyclo-C6H11)2(CF3), HO(cyclo-C6H11)(CF3)2, and HOC(Ar)(CF3)2 (Ar=4-C6H4(t-Bu), 2,4,6-C6H2(CF3)3, 4-Si(i-Pr)3-2,6-C6H2(CF3)2, 3,5-C6H3(CH3)2), and 2-C6H4(C(OH)(CF3)2)
Barbarich, TJ
Nolan, BG
Tsujioka, S
Miller, SM
Anderson, OP
Strauss, SH
JOURNAL OF FLUORINE CHEMISTRY, 2001, 112 (02) : 335 - 342
[9] Radical fluoroalkylthiolation of aldehydes with PhSO2SRf (Rf = CF3, C2F5, CF2H or CH2F): a general protocol for the preparation of fluoroalkylthioesters
Xu, Bin
Li, Dezhi
Lu, Long
Wang, Decai
Hu, Yonghong
Shen, Qilong
ORGANIC CHEMISTRY FRONTIERS, 2018, 5 (14): : 2163 - 2166
[10] Condensation reactions of trifluoronitrosomethane CF3NO with sulfanilamide H2NC6H4SO2NH2 - Preparation of CF3NNC6H4SO2NH2, CF3NNC6H4SO2NNCF3, CH3C(O)N(H)C6H4SO2NNCF3
Minkwitz, Rolf
Jakob, Jens
Winter, Andreas
1997, Verlag der Zeitschrift fur Naturforschung (52):

← 1 2 3 4 5 →