【摘要】 <正> 在（CH₃）₃NO存在下,PPh₃取代M（CO）₅（M=Fe,Ru,Os）中CO的反应速度遵循二级速度定律,分别与[M（CO）₅]和[（CH₃）₃NO]的一次方成正比,与[PPh₃]无关。反应速度按Fe<Ru<Os增大（约增4倍）。这与M₃（CO）₁₂的情况相反,后者按Fe>Ru>Os的次序约减小4倍。 1 实验方法 典型的动力学实验中,将（CH₃）₃NO的C₂H₅OH溶液和PPh₃的己烷溶液分别用注射器加到体积合适的烧瓶中,再注入Fe（CO）₅并迅速震荡烧瓶,再取出一部分反应液立即注入充N₂更多还原

【Abstract】 In this paper the kinetics for CO substitution by PPh3 of M(CO)5(M=Fe,Ru,Os) in the presence of catalytic promoter, (CH3)3NO is reported. The rates of reaction are first-order in concentrations of M(CO)S and of (CH3)3NO but zero-order in PPh3 concentration. The reaction rates show an approximate overall four-fold increase in the order Fe < Ru < Os. This is a contrast to the roughly fourty-fold decrease in rate in the order Fe > Ru > Os for the corresponding metal carbonyl cluster, M3(CO)12.更多还原