有机同秩物概念及单取代烷烃同秩物生成焓和电离能变化规律  

Concept of organic homo-rank compounds and change regularity of enthalpy of formation and ionization potential of homo-rank compounds of mono-substituted alkanes

作　　者：袁华[1] 曹晨忠[1] 武亚新[1] 

机构地区：[1]理论化学与分子模拟教育部重点实验室,分子构效关系湖南省普通高校重点实验室,湖南科技大学化学化工学院,湘潭411201

出　　处：《中国科学：化学》2012年第10期1438-1451,共14页SCIENTIA SINICA Chimica

基　　金：国家自然科学基金(21072053);湖南省教育厅项目(09C386)资助

摘　　要：提出了"有机同秩列"、"有机同秩物"、"有机同秩异构体"等概念体系,并以单取代烷烃同秩物Xi-(CH2)j-H(Xi=F、Cl、Br、I、NO2、CN、NC、OH、NH2、SH、COOH、CHO)为例,对其气相标准摩尔生成焓(△rH■m)、电离能(IP)的结构-性能关系进行了研究,分别对j=2～8的七组同秩物的生成焓及j=2～4的三组同秩物的电离能建立了数学模型:△rH■m(j)=a+b△rH■m(1)+cPEI(R)和IP(j)=a+bIP(1)+bPEI(R),得到了有意义的结果.研究表明,从有机同秩物的角度可以建立一种新的分子结构-性能相关方法,它与有机同系物方法相互独立又互为补充.本文提出的概念体系不仅增加了新的有机化学理论和概念,还为有机物结构-性能变化规律的研究开辟了新视角.Novel concept system including organic homo-rank series, organic homo-rank compounds and organic homo-rank isomers were proposed. Taking homo-rank compounds of mono-substituted alkanes Xi-（CH2）j-H （Xi = F. CI. Br. I. NO2. CN. NC. OH. NH2. SH. COOH. CHO）as example, their structure-property relationships against gas-phase standard molar enthalpy of formation （ △rHm ） and ionization potential （IP） were investigated. Regression models for enthalpy of formation of seven sets of homo-rank compounds with j = 2-8 and ionization potential of three sets of homo-rank compounds withj = 2-4 were built as △r Hm（j） = a ＋ b △rHm（1） ＋ cPEI（R） and IP（）） = a ＋ bIP（1） ＋ bPEI（R）, respectively. This study indicates that a new structure-property relationship approach can be developed from the perspective of organic homo-rank compounds, which is an independent and complementary approach with that based on orgainc homolog compounds. The concept system proposed in this paper not only adds new theory and concept to organic chemistry, but also opens up new perspectives for the study on structure-property change regularity of organic compounds.

关 键 词：有机同秩物 有机同秩列 单取代烷烃 生成焓 电离能 结构-性能相关 

分 类 号：O621.2[理学—有机化学]