| Mo(CO)5L的氧原子转移反应动力学和机理研究 |
| KINETIC AND MECHANISM OF OXYGEN ATOM TRANSFER REACTION TO Mo(CO)5L |
|
| 摘要: 近期我们报道了M(CO)2(M=Cr,Mo,W)与Me2NO反应的动力学研究结果。 本文报道在CH2Cl2,-CH2CN(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+Me3NO+L→顺-Mo(CO)4L2+Me3N+CO3 (1)式中L=P(c-hx)3,P(n-Bu)3,NMe3Pyr,PPh3,AsPh3,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。 |
| 关键词: 氧原子转移反应 动力学 机理 |
| 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 |
| 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. |
| Keywords: oxygen atom transfer reaction kinetic mechaniam |
| 投稿时间：1987-09-25 |
| 摘要点击次数: 1328 |
| 全文下载次数: 1629 |
| 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. |
| 查看全文 查看/发表评论 下载PDF阅读器 |
| Support information: |
|
|
|
|
|
|
