【摘要】 报道了（CH₃）₃NO存在条件下Os₃（CO）₁₂和Os₃（CO）₁1L（L=PPh₃,P（n-Bu）₃,AsPh₃）分别在CH₂Cl₂-C₂H₅OH和CH₂Cl₂溶剂中职代羰基反应的动力学数据。结果表明,反应遵循单项缔合速度定律,与外来配体L的浓度无关。定量地研究了溶剂中乙醇的浓度对反应速度的影响,并讨论了反应机理、过渡态和中间体可能的结构及取代配体的影响。更多还原

【Abstract】 Detailed kinetic data are reported for the reactions of CO substitution of Os3(CO)12 and Os3(CO)11L (where L = PPh3, AsPh3, P(n-Bu)3) in CH2Cl2-C2H5OH and CH2Cl2 respectively in the presence of Me3NO. The results indicate that the reactions follow associative rate law, that is, r = k2[complex][Me3NO], and are independent of entering ligand concentration. The effect of C2H5OH as solvent on the reactions has been investigated quantitatively. Reaction mechanism, structures of transition states and intermediates have been proposed. The ligand effects on the reactions have been discussed as well.更多还原