Mechanistic aspects of formation of chiral ruthenium hydride complexes from 16-electron ruthenium amide complexes and formic acid: Facile reversible decarboxylation and carboxylation
Mechanistic aspects of formation of chiral ruthenium hydride complexes from 16-electron ruthenium amide complexes and formic acid: Facile reversible decarboxylation and carboxylation
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DOI：
10.1002/adsc.200303152
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发表时间：
2004-01-01
影响因子：
5.4
通讯作者：
Ikariya, T
中科院分区：
文献类型：
--
作者：
Koike, T;Ikariya, T
16-电子酰胺络合物Ru[(R,R)TsNCHPhCHPhNH](eta(6)-对伞花烃)(Ts=对甲苯磺酰基，Ph=C6H5)容易与甲酸反应，得到相应的甲酸盐络合物，其随后进行脱羧，导致氢化物络合物并释放CO 2 。该氢化物络合物与CO2的反应在温和的反应条件下，即10个大气压，甚至在-78℃下，反应迅速进行，几乎定量地得到相应的甲酸盐络合物。因此，无论有或没有Ru配合物的金属-NH双功能效应的帮助，都会发生可逆的脱羧和羧化。
The 16-electron amide complex, Ru[(R,R)TsNCHPhCHPhNH](eta(6)-p-cymene) (Ts=p-toluenesulfonyl,Ph=C6H5) readily reacts with formic acid to give the corresponding formate complex, which subsequently undergoes decarboxylation leading to the hydride complex with release Of CO2. The reaction of this hydride complex with CO2 under mild reaction conditions, a pressure of 10 atm and even at -78degreesC, proceeds rapidly to give the corresponding formate complex almost quantitatively. Thus, the reversible decarboxylation and carboxylation takes place with or without the aid of a metal-NH bifunctional effect of the Ru complexes.