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[1]陈姝璇,陈秀梅,吕 鑫*.乙硼烷及其同系物的σ芳香性[J].厦门大学学报(自然科学版),2016,55(03):305-308.[doi:10.6043/j.issn.0438-0479.2016.03.001]
 CHEN Shuxuan,CHEN Xiumei,Lü Xin*.σ-aromaticity in Diborane and Its Congeners[J].Journal of Xiamen University(Natural Science),2016,55(03):305-308.[doi:10.6043/j.issn.0438-0479.2016.03.001]
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《厦门大学学报(自然科学版)》[ISSN:0438-0479/CN:35-1070/N]

卷:
55卷
期数:
2016年03期
页码:
305-308
栏目:
研究论文
出版日期:
2016-05-25

文章信息/Info

Title:
σ-aromaticity in Diborane and Its Congeners
文章编号:
0438-0479(2016)03-0305-04
作者:
陈姝璇陈秀梅吕 鑫*
厦门大学 化学化工学院,固体表面物理化学国家重点实验室,福建省理论与计算化学重点实验室,福建 厦门 361005
Author(s):
CHEN ShuxuanCHEN XiumeiLü Xin*
State Key Laboratory of Physical Chemistry of Solid Surface,Fujian Provincial Key Laboratory of Theoretical and Computational Chemistry,College of Chemistry and Chemical Engineering,Xiamen University,Xiamen 361005,China
关键词:
σ芳香性 缺电子化合物 乙硼烷 多中心键 电子离域
Keywords:
σ-aromaticity electron-deficient compound diborane multicenter bond electron delocalization
分类号:
O 64
DOI:
10.6043/j.issn.0438-0479.2016.03.001
文献标志码:
A
摘要:
本文从理论上证明缺电子乙硼烷及其同系物X2H6(X=B,Al,Ga)中的四元环具有四中心四电子(4c4e)的环状σ共轭体系,尽管看似与休克尔芳香性规则相悖,但具有σ芳香性; 类似地,X2(CH3)6(X=B,Al,Ga)等缺电子甲基化合物也有σ芳香性,但其σ电子离域程度要比相应的氢化物略低; 卤化物X2Y6(X=B,Al,Ga; Y=F,Cl,Br)中四元环的四中心八电子(4c8e)的σ骨架看似与具σ反芳香性的环丁烷相似,但其σ骨架电子均定域于各Y—X σ配键,属非芳香性.
Abstract:
The four-membered rings(4MRs)of electron-deficient X2H6(X=B,Al,Ga)compounds,having a four-center four-electron(4c4e)σ-framework that seemingly conflicts with the(4n+2)e Hückel rule,are shown to be σ-aromatic by means of density functional calculations.The methyl-substituted ones,X2(CH3)6(X=B,Al,Ga),are also σ-aromatic,but with a slightly lower degree of σ electron delocalization than the corresponding hydrides.On the contrary,the 4MRs in the halogen-series X2Y6(X=B,Al,Ga; Y=F,Cl,Br),having a 4c8e σ-framework seemingly similar to that of the σ-antiaromatic cyclobutane,are non-aromatic,as the ring σ-electrons are localized within those Y—X dative bonds.

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备注/Memo

备注/Memo:
收稿日期:2015-11-15 录用日期:2015-11-25
基金项目:国家自然科学基金(21273177); 高等学校博士学科点专项科研基金(20130121110004)
*通信作者:xinlu@xmu.edu.cn
更新日期/Last Update: 1900-01-01