Strong Activation of the Double Bond in (PPh<sub>2</sub>)<sub>2</sub>CCH<sub>2</sub>. Novel Synthesis of Gold(III) Methanide Complexes by Michael Addition Reactions
作者:Eduardo J. Fernández、M. Concepción Gimeno、Peter G. Jones、Antonio Laguna、Elena Olmos
DOI:10.1021/om9609832
日期:1997.3.1
vinylidenebis(diphenylphosphine), (PPh2)2CCH2, leads to the complex [Au(C6F5)2ClPPh2C(CH2)PPh2}]. The coordination of the diphosphine to a gold(III) center strongly activates the carbon−carbon double bond, and this complex, therefore, undergoes Michael-type additions with several carbon-, sulfur-, or oxygen-based nucleophiles. The complexes [Au(C6F5)2(PPh2)2CCH2SPh}], [Au(C6F5)2(PPh2)2CCH2S2CNEt2}]
用亚乙烯基双(二苯基膦),(PPh 2)2 C CH 2处理[Au(μ-Cl)(C 6 F 5)2 ] 2,生成络合物[Au(C 6 F 5)2 Cl PPh 2 C(CH 2)PPh 2 }]。二膦与金(III)中心的配位作用会强烈激活碳-碳双键,因此该配合物会经历迈克尔型加成反应,并带有几个基于碳,硫或氧的亲核试剂。络合物[Au(C 6 F 5)2 (PPh2)2 CCH 2 SPh}],[Au(C 6 F 5)2 (PPh 2)2 CCH 2 S 2 CNEt 2 }]和[Au(C 6 F 5)2 (PPh 2)2已经通过X射线衍射分析对CCH 2 }} 2 O]进行了结构表征。他们表明加成反应发生在双键的末端碳原子上,生成了甲烷化物型配合物。此外,[Au(C 6 F 5)中的醚分子的置换2(OR 2)2 ] ClO 4(R = Et,i Pr)通过二膦一锅合成得到配合物[Au(C