期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 137, 期 24, 页码 7921-7928出版社
AMER CHEMICAL SOC
DOI: 10.1021/jacs.5b04613
关键词
-
资金
- NIHGMS [RO1 GM073932]
- NIH [F32 GM103238-02, S10- RR027172]
- NSF [DGE 1106400]
Two unique organometallic halide series (Ph3P)Au(4-Me-C6H4)(CF3)(X) and (Cy3P)Au(4-F-C6H4)(CF3)(X) (X = I, Br, Cl, F) have been synthesized. The PPh3-supported complexes can undergo both CarylX and C-aryl-CF3 reductive elimination. Mechanistic studies of thermolysis at 122 degrees C reveal a dramatic reactivity and kinetic selectivity dependence on halide ligand. For X = I or F, zero-order kinetic behavior is observed, while for X = Cl or Br, kinetic studies implicate product catalysis. The selectivity for C-aryl-CF3 bond formation increases in the order X = I < Br < Cl < F, with exclusively C-aryl-I bond formation when X = I, and exclusively C-aryl-CF3 bond formation when X = F. Thermodynamic measurements show that Au(III)-X bond dissociation energies increase in the order X = I < Br < Cl, and that ground state Au(III)-X bond strength ultimately dictates selectivities for C-aryl-X and C-aryl-CF3 reductive elimination.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据