Coupling of two ethyne molecules at rhodium versus coupling of two rhodium atoms at ethyne. 2. Implications for the reactivity. Catalytic and stoichiometric functionalization reactions of ethyne
Coupling of two ethyne molecules at rhodium versus coupling of two rhodium atoms at ethyne. 2. Implications for the reactivity. Catalytic and stoichiometric functionalization reactions of ethyne
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两个乙炔分子在铑上的偶联与两个铑原子在乙炔上的偶联。
DOI：
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发表时间：
1991
期刊：
影响因子：
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通讯作者：
F. Vizza
中科院分区：
文献类型：
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作者：
C. Bianchini;A. Meli;M. Peruzzini;A. Vacca;F. Vizza
通过在CH 2 Cl 2 中用过量乙炔处理[(triphos)RhCl(C 2 H 4 )] (1) (triphos=MeC(CH 2 PPh 2 ) 3 )，合成了铑环戊二烯络合物[(triphos)RhCl(η 2 -C 4 H 4 )] (3)。配合物3在非常温和的条件下催化乙炔环三聚成苯以及乙炔与乙腈环共低聚成2-甲基吡啶。基于多种形式的实验证据，提出了两种反应的合理催化循环。 3 的化学性质与相关的垂直 μ-C 2 H 2 配合物 [(triphos)Rh(μ-Cl)(μ-η 2 ,η 2 -C 2 H 2 )Rh(triphos)] Cl 进行了比较和对比 (2)
The rhodacyclopentadiene complex [(triphos)RhCl(η 2 -C 4 H 4 )] (3) has been synthesized by treatment of [(triphos)RhCl(C 2 H 4 )] (1) in CH 2 Cl 2 with an excess of ethyne (triphos=MeC(CH 2 PPh 2 ) 3 ). Complex 3 catalyzes under very mild conditions the cyclotrimerization of ethyne to benzene as well as the cyclocooligomerization of ethyne with acetonitrile to 2-picoline. A plausible catalysis cycle for both reactions is proposed on the basis of multiform experimental evidence. The chemistry of 3 has been compared to and contrasted with that of the related perpendicular μ-C 2 H 2 complex [(triphos)Rh(μ-Cl)(μ-η 2 ,η 2 -C 2 H 2 )Rh(triphos)] Cl (2)