有机张力分子弯键特征的理论研究  

Theoretical Studies on Bent Bond, Strain and Bonding Behavior of Strained Organic Molecules

作　　者：赵存元[1] 邱文元[1] 许先芳[1] 张昌言[1] 方维海[1] 游效曾[1] 

机构地区：[1]西北师范大学化学系,兰州大学化学系,南京大学配位化学研究所

出　　处：《高等学校化学学报》1995年第10期1587-1591,共5页Chemical Journal of Chinese Universities

基　　金：甘肃省自然科学基金

摘　　要：提出了任意张力分子中弯键特征的计算公式，对一系列典型的有机张力分子──单环烃、双环烃、螺桨烷、多面体烷及部分不饱和环状烃的结构、张力、稳定性及反应性之间的关系进行了研究，其弯键特征的理论研究表明：有机张力分子的Ｃ－Ｃ键均发生不同程度弯曲，且Ｃ－Ｃ弯键之间的夹角与四面体杂化角度１０９．５°的差值△β可成为有机分子张力与稳定性的量度。The calculation formulae of the bent bond and strain characteristics in any strained organic molecules are proposed. The relationship among structure, strain, stability and reactivity on 38 typical hydrocarbons-cyclic, bicyclic hydrocarbons, propellanes, polyhedranes and some unsaturated hydrocarbons has been revealed:(a)the C-C bond of strained organic molecules with three-or four-membered rings are much greater than those with five-or six-membered rings,(b) the bond length of bent bonds in strained organic molecules is less than that of acyclic hydrocarbons. The bond length increases with the increase of ring size and the decrease of bent angles. The bond length of C-C bonds in polyhedroang increases with the increase of the size of polyhedral framework;(c) the real bond angles (defined as equation 7 in the paper) have a tendency towards tetrahedral angle 109.5°,whatever the bent angle(0-32°) and bond angles(60-140°)are greater or small. The real bond angles of high strained organic molecules are much more greatly deviated from the tetrahedral angle 109.5°than those of less strained or strainless molecules. However, the real bond angles H-C-H or H-C-C of three-membered rings have a tendency towards the angle 120°rather than 109.5°, It can be concluded that the deviaton(△β) of bent bond angles from the tetrahedral angles 109.5°can be used to evaluate the molecular strain and stability.

关 键 词：弯键特征 张力分子 单环烃 双环烃 

分 类 号：O621.14[理学—有机化学]