| Mo(CO)5L的氧原子转移反应动力学和机理研究 |
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| 引用本文： | 高忆慈,史启祯,David L. Kershner,Fred Basolo. Mo(CO)5L的氧原子转移反应动力学和机理研究[J]. 无机化学学报, 1989, 5(2): 112-116 |
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| 作者姓名： | 高忆慈 史启祯 David L. Kershner Fred Basolo |
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| 作者单位： | 兰州大学化学系 兰州(高忆慈，史启祯)，美国西北大学化学系 美国(David L.Kershner)，美国西北大学化学系 美国(Fred Basolo) |
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| 基金项目： | 属中美合作科研项目内容，得到中国自然科学基金委员，美国国家科学基金会的资助 |
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| 摘 要： | 近期我们报道了M(CO)_2(M=Cr,Mo,W)与Me_2NO反应的动力学研究结果。 本文报道在CH_2Cl_2,-CH_2CN(体积比1:1)混合溶剂中,三甲胺氧化物存在下的二取代反应: Mo(CO)_5L Me_3NO L→顺-Mo(CO)_4L_2 Me_3N CO_3 (1)式中L=P(c-hx)_3,P(n-Bu)_3,NMe_3Pyr,PPh_3,AsPh_3,P(OEt)和P(OMe)_3,在金属原子不变的情况下对配体的电子效应(以Mo(CO)_5L的羰基伸缩振动频率表现出来)和立体效应做探讨。
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| 关 键 词： | 氧原子转移反应 动力学 机理 |
| 收稿时间： | 1987-09-25 |
KINETIC AND MECHANISM OF OXYGEN ATOM TRANSFER REACTION TO Mo(CO)5L |
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| Gao Yici,Shi Qizhen,David L. Kershncr and Fred Basolo. KINETIC AND MECHANISM OF OXYGEN ATOM TRANSFER REACTION TO Mo(CO)5L[J]. Chinese Journal of Inorganic Chemistry, 1989, 5(2): 112-116 |
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| Authors: | Gao Yici Shi Qizhen David L. Kershncr Fred Basolo |
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| Affiliation: | Department of chemistry, Lanzhou University, Lanzhou,Department of chemistry, Lanzhou University, Lanzhou,Department of chemistry, Northwestern University, U.S.A and Department of chemistry, Northwestern University, U.S.A |
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| Abstract: | In this paper kinetic data are reported for the reaction of Mo(CO)5L,(where L=P(c-hx)3,P(n-Bu)3,NMe3,Pyr,PPh3,AsPh3 or P(OMe)3) with L in the presence of Me3NO to form cis-Mo(CO)4L2.The CO substitution in Mo(CO)5L obeys a second-order rate law that is first order in both Mo(CO)5L and Me3NO. Activation parameters further support the associative nature of the reaction. For ligand L with cone angles less than 135°,the rates of reaction increase with increasing stretching frequency of the CO bands in the IR. This supports the proposed mechanism which involves attack by the O atom of Me3NO on a C of a CO cis to L in Mo(CO)5L and indicates the electronic effects at the C atoms of CO are more important than steric effects in these reactions for complexes. |
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| Keywords: | oxygen atom transfer reaction kinetic mechaniam |
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