铁(Ⅱ)异腈配合物与三甲基胺氮氧化物氧原子转移反应动力学及其机理研究  

Kinetics and Mechanism of Oxygen Atom Transfer Reactions between Iron(Ⅱ) Isocyanide Complexes and (CH_3)_3NO

作　　者：何宏山[1] 高忆慈[2] 史启祯[3] 

机构地区：[1]华侨大学材料科学与工程学院,福建泉州362011 [2]兰州大学化学与化工学院,甘肃兰州7300003 [3]西北大学化学系,陕西西安710069

出　　处：《光谱学与光谱分析》2003年第1期9-13,共5页Spectroscopy and Spectral Analysis

摘　　要：在CH2 Cl2 介质中研究了铁 (Ⅱ )异腈配合物 [FeL5(CN) ]Br(1 ,L = CNCH2 Ph)和trans [FeL4(CN) 2 ] (2 ,L = CNCH2 Ph)等与氧原子转移试剂 (CH3) 3NO的反应动力学行为 ,研究结果表明 :配合物 1与 (CH3) 3NO反应遵从二级速率定律 ,反应速率 =k2 [铁异腈配合物 ]× [(CH3) 3NO]。反应的活化熵ΔS≠ 和活化焓ΔH≠ 分别为- 2 5 34± 1 67cal·(mol·K) - 1 和 1 2 71± 0 49kcal·mol- 1 ,而配合物 2不与氧原子转移试剂反应。认为反应以缔合机理进行。Kinetics and mechanism of reactions between iron(Ⅱ) isocyanide complexes [FeL 5(CN)]Br (1, L=-CNCH2Ph); trans-[FeL 4(CN) 2] 2, L=-CNCH 2Ph) and oxygen atom transfer agent (CH 3) 3NO have been investigated in dichloromethane by UV-visible and Infrared spectrophotometers at different temperatures. The results revealed that the reactions proceed with second order and the rate law is rate=k 2[isocyanide complex]×[(CH 3) 3NO].ΔS≠ and ΔH≠ for the reaction between complex 1 and (CH 3) 3NO are -25.34±1.67 cal·(mol·K) -1 and 12.71±0.49 kcal·mol -1 respectively. However, there is no reaction between 2 and (CH 3) 3NO. The reaction mechanism was proposed and the factors affecting the reaction rate were also discussed.

关 键 词：铁(Ⅱ) 异腈配合物 三甲基胺氮氧化物 氧原子转移反应 反应动力学 反应机理 

分 类 号：O614.811[理学—无机化学] O643.1[理学—化学]