| 硼氢化反应机理Ⅴ——HOMO-HOMO相互作用对有机腈类硼氢化反应的影响(英文) |
| |
| 引用本文： | 崔瑞海,孙志忠,范卓文.硼氢化反应机理Ⅴ——HOMO-HOMO相互作用对有机腈类硼氢化反应的影响(英文)[J].分子科学学报,1999(2). |
| |
| 作者姓名： | 崔瑞海 孙志忠 范卓文 |
| |
| 作者单位： | 哈尔滨师范专科学校(崔瑞海)，黑龙江大学(孙志忠)，黑龙江中医药大学(范卓文) |
| |
| 摘 要： | 利用量子化学从头计算法ＲＨＦ／ＳＴＯ－３Ｇ基组对甲基腈和氢氰酸硼氢化反应进行了理论研究。微扰分子轨道理论分析表明：在甲基腈硼氢化反应中，过渡态的ＨＯＭＯ是由ＨＯＭＯ－ＬＵＭＯ相互作用和ＨＯＭＯ－ＨＯＭＯ相互作用形成的。通过与氢氰酸硼氢化反应的比较，即考虑甲基对ＨＯＭＯ－ＨＯＭＯ相互作用的影响，可知供电子基团能提升ＨＯＭＯ的能级进而增加了有机腈类硼氢化反应的速度
|
| 关 键 词： | 甲基腈 硼氢化反应 HOMO-HOMO相互作用 |
Reaction Mechanism of Hydroboration The Effect of HOMO-HOMO Interactions on the Hydroboration Reaction of Organic Nitriles |
| |
| Cui RuihaiSun ZhizhongFan Zhuowen.Reaction Mechanism of Hydroboration The Effect of HOMO-HOMO Interactions on the Hydroboration Reaction of Organic Nitriles[J].Journal of Molecular Science,1999(2). |
| |
| Authors: | Cui RuihaiSun ZhizhongFan Zhuowen |
| |
| Affiliation: | Cui Ruihai1Sun Zhizhong2Fan Zhuowen3 |
| |
| Abstract: | The transition states for the reactions of methyl cyanide and hydrocyanic acid with borane are calculated at the restricted SCF level by using the STO-3G basis set. Perturbational Molecular Theory analysis of these transition states reveals their HOMOs to be formed from both HOMO-LUMO interaction and HOMO-HOMO interaction. The general importance of the HOMO-HOMO interaction of the organic nitriles is also shown by the comparison between the FMO for the hydroboration reaction of methyl cyanide and the FMO for the hydroboration reaction of hydrocyanic acid. The effect of a methyl group on the HOMO-HOMO interaction of the organic nitriles is also shown by the comparison between the FMO for the hydroboration reaction of methyl cyanide and the FMO for the hydroboration reaction of hydrocyanic acid. The effect of a methyl group on the HOMO-HOMO interaction indicates that an electron-donating group can raise the energy of the HOMO and increase the rate of the hydroboration reactions of the organic nitriles. |
| |
| Keywords: | methyl cyanide hydroboration HOMO-HOMO interaction |
| 本文献已被 CNKI 等数据库收录！ |
