DESIGN OF BRIDGED POLYCYCLIC DIOLEFIN PRECURSORS FOR PRISMANES USING FMO ORDER AS CRITERIA - INTERBRIDGE DISTANCE AS A NEW FACTOR FOR CONTROLLING THE INTRAMOLECULAR [PI-2+PI-2] CYCLOADDITION

被引：10

作者：

CHA, OJ ^{[1
]}

OSAWA, E ^{[1
]}

PARK, S ^{[1
]}

机构：

[1] TOYOHASHI UNIV TECHNOL,DEPT KNOWLEDGE BASED INFORMAT ENGN,TEMPAKU CHO,TOYOHASHI 441,JAPAN

来源：

JOURNAL OF MOLECULAR STRUCTURE | 1993年 / 300卷

关键词：

D O I：

10.1016/0022-2860(93)87007-V

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

If alkylene bridges of appropriate length are strategically spanned across their juxtaposed double bonds, it may be possible to effect [pi2 + pi2] photochemical cycloaddition of hypostrophene and homologous polycyclic diolefins leading to penta- and hexaprismane derivatives. Frontier molecular orbital (FMO) criteria were used to assess the possibilities of such syntheses. FMO orders were interpreted in terms of the formalism of pi/sigma orbital interactions through space and/or bonds. Cases that do not follow this formalism were explained by invoking a new factor, the interbridge distance (d2). Replacement of the trimethylene bridge by -CH2OCH2- was found to be effective in enlarging the energy gaps between the FMOs.

引用

页码：73 / 81

页数：9

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