TRANSANNULAR INTERACTIONS IN POLYCYCLIC HYDROCARBONS. THE SYSTEM OF CAGE-SHAPED HEXACYCLO[6.6.0.0(2,6).0(3,13).0(4,11).0(5,9)]TETRADECANE DERIVATIVES

被引:11
作者
CHOW, TJ
WEI, CC
WU, TK
MARTIN, HD
MAYER, B
机构
[1] ACAD SINICA,INST CHEM,TAIPEI,TAIWAN
[2] UNIV DUSSELDORF,INST ORGAN CHEM & MAKROMOLEK CHEM,D-40225 DUSSELDORF,GERMANY
关键词
D O I
10.1021/jo00122a055
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
The gas phase He(I alpha) photoelectron spectra (PES) of several ketone and olefinic derivatives of the titled compound are measured. The high energy pi-orbitals (HOMO and SHOMO) of 1e show an unusually large energy splitting of 0.90 eV, while the corresponding n-orbitals of 1d appear to be nearly degenerate (<0.1 eV). The difference between these observations is analyzed with the aid of theoretical models. It is concluded in this work that the pi-pi energy splitting of 1e is derived mainly from an orbital interaction transmitted through-space (TS) across the ring. Since such a nonbonded interaction is sensitive to distance, a conformational analysis of the cycloctane ring moiety of 1e is also performed. As compared to the result of PES, it seems that the ab initio (STO-3G) method is more reliable than AM1, in which the TS interaction is somewhat underestimated.
引用
收藏
页码:5651 / 5657
页数:7
相关论文
共 42 条
[1]   SMALL AND MEDIUM RINGS .78. CAGE DIMERS OF NORBORNADIENE WITH PERPENDICULAR ARRANGEMENT OF SUBCHROMOPHORES - ORBITAL INTERACTION IN THE HEPTACYCLO (6.6.0.0(2,6).0(3,13).0(4,11).0(5,9).0(10,14))TETRADECANE SYSTEM [J].
ALBERT, B ;
ELSASSER, D ;
MARTIN, HD ;
MAYER, B ;
CHOW, TJ ;
MARCHAND, AP ;
REN, CT ;
PADDONROW, MN .
CHEMISCHE BERICHTE-RECUEIL, 1991, 124 (12) :2871-2878
[2]   SMALL AND MEDIUM RINGS .75. SYNTHESES, PHOTOELECTRON-SPECTRA, AND PHOTOREACTIVITY OF POLYCYCLIC 1,5-DIKETONES - TRANSANNULAR INTERACTION IN THE CYCLOOCTANE-1,5-DIONE FRAGMENT [J].
ALBERT, B ;
ELSASSER, D ;
HECKEL, D ;
KOPMEIER, S ;
MARTIN, HD ;
MAYER, B ;
CHOW, TJ ;
WU, TK ;
YEH, SK .
CHEMISCHE BERICHTE, 1991, 124 (04) :803-813
[3]  
ALLINGER NL, 1991, MM2
[4]  
ASBRINK L, 1977, CHEM PHYS LETT, V52, P61
[5]  
BARTETZKO R, 1979, J AM CHEM SOC, V100, P5589
[6]   APPLICATION OF EQUIVALENT BOND ORBITAL MODEL TO C2S-IONIZATION ENERGIES OF SATURATED-HYDROCARBONS [J].
BIERI, G ;
DILL, JD ;
HEILBRONNER, E ;
SCHMELZER, A .
HELVETICA CHIMICA ACTA, 1977, 60 (07) :2234-2247
[7]  
BIRD CW, 1961, TETRAHEDRON LETT, P373
[8]  
BURKERT U, 1982, ACS MONOGRAPHS AM CH, V177
[9]   FORMATION OF VINYLSILANES AND ALLYLSILANES IN THERMAL ELIMINATION-REACTIONS OF ESTERS OF BETA-HYDROXYALKYLTRIMETHYLSILANES [J].
CAREY, FA ;
TOLER, JR .
JOURNAL OF ORGANIC CHEMISTRY, 1976, 41 (11) :1966-1971
[10]   SYNTHESIS OF ALKENES FROM CARBONYL-COMPOUNDS AND CARBANIONS ALPHA TO SILICON .3. FULL REPORT AND A SYNTHESIS OF SEX-PHEROMONE OF GYPSY MOTH [J].
CHAN, TH ;
CHANG, E .
JOURNAL OF ORGANIC CHEMISTRY, 1974, 39 (22) :3264-3268