Strong activation of the double bond in (PPh(2))(2)C=CH2. Novel synthesis of gold(III) methanide complexes by Michael addition reactions

被引:11
作者
Fernandez, EJ
Gimeno, MC
Jones, PG
Laguna, A
Olmos, E
机构
[1] UNIV ZARAGOZA, CSIC, INST CIENCIA MAT ARAGON, DEPT QUIM INORGAN, E-50009 ZARAGOZA, SPAIN
[2] UNIV LA RIOJA, DEPT QUIM, E-26001 LOGRONO, SPAIN
[3] TECH UNIV CAROLO WILHELMINA BRAUNSCHWEIG, INST ANORGAN & ANALYT CHEM, D-38023 BRAUNSCHWEIG, GERMANY
关键词
D O I
10.1021/om9609832
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Treatment of [Au(mu-Cl)(C6F5)(2)](2) with vinylidenebis(diphenylphosphine), (PPh(2))(2)C=CH2, leads to the complex [Au(C6F5)(2)Cl{PPh(2)C(=CH2)PPh(2)}]. 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){PPh(2))(2)(CCH(2)SPh}], [Au(C6F5)(2){(PPh(2))(2)CCH2S2-CNEt(2)}], and [{Au(C6F5)(2){(PPH2)(2)CCH2}}(2)O] have been structurally characterized by X-ray diffraction analysis. They show that the addition has taken place at the terminal carbon atom of the double bond, giving methanide-type complexes. Furthermore, the displacement of the ether molecules in [Au(C6F5)(2)(OR(2))(2)]ClO4 (R = Et, Pr-i) by the diphosphine leads, in a one pot synthesis, to the complexes [Au(C6F5)(2){(PPh(2))(2)CHCH(2)OR}]ClO4 as a consequence of ether cleavage by water.
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页码:1130 / 1136
页数:7
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