DNMR 研究金属烯烃内质子交换的动力学行为

华东师范大学学报(自然科学版) ›› 2003, Vol. 2003 ›› Issue (2): 46-53.

DNMR 研究金属烯烃内质子交换的动力学行为

张贵荣¹； Stephen Matchett²; 戴立益¹；陆嘉星^1*

1 华东师范大学化学系，上海 200062； 2 美国大河谷州立大学， Allendale MI49401,美国

收稿日期:2002-05-09 修回日期:2002-10-19 出版日期:2003-04-15 发布日期:2003-04-15

Studies of the Relationship between Proton Chemical Exchange and Substituent Electronic Effects in Some Metal-Olefin with DNMR

ZHANG Gui-rong¹； Stephen Matchett²; DAI Li-yi¹ ; LU Jia-xing¹

1 Department of Chemistry, East China Normal University, Shanghai 200062, China 2 Grand Valley State University, Allendale, MI49401,USA

Received:2002-05-09 Revised:2002-10-19 Online:2003-04-15 Published:2003-04-15

摘要/Abstract

摘要： 该文用完全线形分析法、磁化强度迁移法和自选锁定技术等三种具体的DNMR法对含有不同取代基的金属烯烃有机化合物中因碳碳键转动引起的分子内质子的化学交换的动力学行为进行了较为详细的研究。结果表明，测得的化学交换的速率常数是合理的。它们满足Eyring 和Ar-rehenuius 关系式；由此获得的化学交换的活化能参数和活化自由能的变化与化合物中的取代基的Hammett 常数6存在很好的一致关系。

关键词: 线形拟合, 磁化强度, 自旋锁定, DNMR, 活化能, 化学交换, 线形拟合, 磁化强度, 自旋锁定, DNMR, 活化能, 化学交换

Abstract: The proton chemical exchanges, created by the rotation of carbon-carbon bond in some Metal-Olefines, were examined with three methods of Dynamic Nuclear Magnetic Resonance. They are Complete Line-shape Analysis, Magnetization Transfer and Spin-Lock. The rate constants of these chemical exchange trends with the Hammett constant of substituents in the Metal-Olefins studied.

Key words: magnetization transfer, spin-lock, DNMR, chemical exchange, complete line-shape analysis, magnetization transfer, spin-lock, DNMR, chemical exchange

张贵荣;Stephen Matchett;戴立益;陆嘉星*. DNMR 研究金属烯烃内质子交换的动力学行为[J]. 华东师范大学学报(自然科学版), 2003, 2003(2): 46-53.

ZHANG Gui-rong;Stephen Matchett;DAI Li-yi;LU Jia-xing. Studies of the Relationship between Proton Chemical Exchange and Substituent Electronic Effects in Some Metal-Olefin with DNMR[J]. Journal of East China Normal University(Natural Sc, 2003, 2003(2): 46-53.