Novel Diborane-Analogue Transition Structures for Borane Reactions with Alkyl Halides

Lawrence M.Pratt; Ngan Van Nguyen

首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Novel Diborane-Analogue Transition Structures for Borane Reactions with Alkyl Halides

【24h】

Novel Diborane-Analogue Transition Structures for Borane Reactions with Alkyl Halides

机译：硼烷与烷基卤化物反应的新型乙硼烷-模拟过渡结构

获取原文

获取原文并翻译 | 示例

掌桥外文数据库（机构版） >>

开具论文收录证明 >>

文献代查 >>

页面导航

摘要
著录项
相似文献
相关主题

摘要

Ab initio and DFT calculations were performed to examine the mechanisms of reduction of alkyl halides and formaldehyde by borane.With alkyl halides,the optimized transition structure geometry resembled diborane,with a pair of hydrogen atoms bridging the boron and carbon atoms by three-center-two-electron bonds.A similar transition structure was found for the reduction of formaldehyde,although it was not the lowest-energy transition structure.Solvation by dimethyl ether or dimethyl sulfide disrupted this bridging with chloromethane,while both ligands dissociated from borane during the reduction of formaldehyde.The high calculated activation free energies of alkyl halide reduction are consistent with their observed lack of reactivity with borane.

机译：进行了从头算和DFT计算，研究了硼烷还原烷基卤和甲醛的机理。对于烷基卤，优化的过渡结构的几何形状类似于乙硼烷，一对氢原子通过三个中心将硼和碳原子桥接尽管不是最低能量的过渡结构，但仍发现了相似的过渡结构可用于甲醛还原。二甲醚或二甲基硫醚的溶剂化作用破坏了与氯甲烷的桥连，而在还原过程中两个配体均从硼烷中解离烷基卤还原的高计算活化自由能与其观察到的与硼烷缺乏反应性相一致。

著录项

来源
《The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory》 |2006年第2期|共4页
作者
Lawrence M.Pratt; Ngan Van Nguyen;
展开▼
作者单位

展开▼
收录信息
原文格式 PDF
正文语种 eng
中图分类
关键词

相似文献

外文文献
中文文献
专利

1. Novel Diborane-Analogue Transition Structures for Borane Reactions with Alkyl Halides [J] . Lawrence M.Pratt, Ngan Van Nguyen The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory . 2006,第2期

机译：硼烷与烷基卤化物反应的新型乙硼烷-模拟过渡结构
2. Reactions of amino-imino-boranes with transition metal halides and substituted transition metal halides [J] . Bock B., Wietelmann U., Noth H. Zeitschrift fur Naturforschung, B. A Journal of Chemical Sciences . 2001,第7期

机译：氨基亚氨基硼烷与过渡金属卤化物和取代的过渡金属卤化物的反应
3. How Alkyl Halide Structure Affects E2 and S_N2 Reaction Barriers: E2 Reactions Are as Sensitive as S_N2 Reactions [J] . Paul R. Rablen, Brett D. McLarney, Brandon J. Karlow, The Journal of Organic Chemistry . 2014,第3期

机译：卤代烷的结构如何影响E2和S_N2反应的障碍：E2反应与S_N2反应一样敏感
4. Reduction of alkyl halides by electrogenerated cobalt(I) salen and nickel(I) salen: reactions of alkyl radicals with no and O_2 [C] . Dennis G. Peters, Chang Ji, Benjamin J. Wozniak, International Manuel M. Baizer Symposium . 2002

机译：通过电子化钴（I）盐和镍（I）盐来减少烷基卤化物：烷基的反应没有NO和O_2
5. The study of liquid solution and solid phase systems: I. Reactions and thermodynamics of alkyl halides. II. Structures and energetics of group 13-15 compounds. [D] . Kormos, Bethany Lyn. 2004

机译：液相和固相系统的研究：I.卤代烷的反应和热力学。二。 13-15组化合物的结构和能量。
6. Non-enzymatic and enzymatic hydrolysis of alkyl halides: A haloalkane dehalogenation enzyme evolved to stabilize the gas-phase transition state of an SN2 displacement reaction [O] . Felice C. Lightstone, Ya-Jun Zheng, Andreas H. Maulitz, 1997

机译：烷基卤的非酶水解和酶水解：卤代烷脱卤酶的发展是为了稳定SN2置换反应的气相过渡态
7. Nickel-catalyzed Suzuki-Miyaura reactions of unactivated halides with alkyl boranes and planar-chiral borabenzene catalysts for Diels-Alder reactions [O] . Lu Zhe 2010

机译：用于Diels-alder反应的未催化卤化物与烷基硼烷和平面手性硼苯催化剂的镍催化suzuki-miyaura反应

Novel Diborane-Analogue Transition Structures for Borane Reactions with Alkyl Halides

摘要

著录项

相似文献

相关主题

期刊订阅