动力学同位素效应证据表明，在由[p-(Me2CH)C6H4Me]Ru-(NHCHPhCHPhNSO2C6H4-p-CH3)催化的转移氢化反应中存在协同氢转移机制。
Kinetic isotope effect evidence for a concerted hydrogen transfer mechanism in transfer hydrogenations catalyzed by [p-(Me2CH)C6H4Me]Ru- (NHCHPhCHPhNSO2C6H4-p-CH3).
作者信息
Casey Charles P, Johnson Jeffrey B
机构信息
Department of Chemistry, University of Wisconsin-Madison, Madison, Wisconsin 53706, USA.
出版信息
J Org Chem. 2003 Mar 7;68(5):1998-2001. doi: 10.1021/jo0205457.
The isotope effects in the reaction of [p-(Me2CH)C6H4Me]Ru(NHCHPhCHPhNSO2C6H4-p-CH3) (1) with isopropyl alcohol were 1.79 for transfer of hydrogen from OH to N and 2.86 for transfer from CH to Ru. The isotope effect for transfer of deuterium from doubly labeled material (kCHOH/kCDOD = 4.88) was within experimental error of the product of the two individual isotope effects. These isotope effects provide convincing evidence for a mechanism involving concurrent transfer of hydrogen from oxygen to nitrogen and from carbon to ruthenium.
[p-(二甲基环己基)C6H4Me]Ru(NHCHPhCHPhNSO2C6H4-p-CH3) (1)与异丙醇反应中的同位素效应，对于氢从OH转移至N为1.79，对于从CH转移至Ru为2.86。来自双标记物质的氘转移的同位素效应(kCHOH/kCDOD = 4.88)在两个单独同位素效应乘积的实验误差范围内。这些同位素效应为涉及氢从氧同时转移至氮以及从碳转移至钌的机理提供了令人信服的证据。
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