| Os_3(CO)_(12)及其膦取代衍生物氧原子转移反应动力学与机理研究 |
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| 引用本文： | 申建坤,高忆慈,史启祯,Fred Basolo.Os_3(CO)_(12)及其膦取代衍生物氧原子转移反应动力学与机理研究[J].高等学校化学学报,1988(10). |
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| 作者姓名： | 申建坤 高忆慈 史启祯 Fred Basolo |
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| 作者单位： | 兰州大学化学系
(申建坤，高忆慈，史启祯)，美国西北大学化学系(Fred Basolo) |
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| 基金项目： | 中国自然科学基金，美国国家科学基金 |
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| 摘 要： | 报道了(CH_3)_3NO存在条件下Os_3(CO)_(12)和Os_3(CO)_11L(L=PPh_3,P(n-Bu)_3,AsPh_3)分别在CH_2Cl_2-C_2H_5OH和CH_2Cl_2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。
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| 关 键 词： | 十二羰基合三锇 三甲基胺氧化物 氧原子转移 动力学与机理 |
Kinetics and Mechanism of Oxygen Atom Transfer Reactions to Os_3(CO)_12 and Its Phosphine Substituted Derivatives |
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| Shen Jiankun,Gao Yici.Shi Qizhen.Kinetics and Mechanism of Oxygen Atom Transfer Reactions to Os_3(CO)_12 and Its Phosphine Substituted Derivatives[J].Chemical Research In Chinese Universities,1988(10). |
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| Authors: | Shen Jiankun Gao YiciShi Qizhen |
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| 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 = k2complex]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. |
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| Keywords: | Triosmium dodecacarbonyl Trimethylamine N-Oxide Oxygen atom transfer Kinetics and mechanism |
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