Synthesis and Study of Cationic, Two-Coordinate Triphenylphosphine- Gold-Complexes

被引：42
|
作者：
Brooner, Rachel E. M. [1 ]
Brown, Timothy J. [1 ]
Widenhoefer, Ross A. [1 ]
机构：
[1] Duke Univ, Dept Chem, French Family Sci Ctr, Durham, NC 27708 USA
来源：
CHEMISTRY-A EUROPEAN JOURNAL | 2013年 / 19卷 / 25期
基金：
美国国家科学基金会;
关键词：
alkene ligands; allenes; diene ligands; gold; complexes; DYNAMIC SOLUTION BEHAVIOR; RAY CRYSTAL-STRUCTURES; INTERMOLECULAR HYDROAMINATION; STRUCTURAL-CHARACTERIZATION; HIGHLY EFFICIENT; BOND; REACTIVITY; CATALYSIS;
D O I：
10.1002/chem.201204564
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
Cationic, two-coordinate triphenylphosphine-gold(I)-complexes of the form [(PPh3)Au(ligand)]+ SbF6- (ligand=4-methylstyrene, 1SbF6), 2-methyl-2-butene (3SbF6), 3-hexyne (6SbF6), 1,3-cyclohexadiene (7SbF6), 3-methyl-1,2-butadiene (8SbF6), and 1,7-diphenyl-3,4-heptadiene (10SbF6) were generated in situ from reaction of [(PPh3)AuCl], AgSbF6, and ligand at -78 degrees C and were characterized by low-temperature, multinuclear NMR spectroscopy without isolation. The ligands of these complexes were both weakly bound and kinetically labile and underwent facile intermolecular exchange with free ligand (G approximate to 9kcalmol-1 in the case of 6SbF6) and competitive displacement by weak sigma donors, such as trifluoromethane sulfonate. Triphenylphosphine-gold(I)-complexes were thermally unstable and decomposed above -20 degrees C to form the bis(triphenylphosphine) gold cation [(PPh3)2Au]+SbF6- (2SbF6).
引用
收藏
页码：8276 / 8284
页数：9
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