SMALL-RING CYCLIC CUMULENES - THEORETICAL-STUDIES OF THE STRUCTURE AND BARRIER TO INVERSION IN CYCLIC ALLENES
SMALL-RING CYCLIC CUMULENES - THEORETICAL-STUDIES OF THE STRUCTURE AND BARRIER TO INVERSION IN CYCLIC ALLENES
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DOI：
10.1021/ja00289a002
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发表时间：
1985-01-01
影响因子：
15
通讯作者：
JOHNSON, RP
中科院分区：
文献类型：
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作者：
ANGUS, RO;SCHMIDT, MW;JOHNSON, RP
描述了 1, 2-环戊二烯和 1, 2-环己二烯的从头计算 SCF、MCSCF 和 Moller-Plesset 计算的结果。 1, 2-环己二烯经计算更倾向于手性联烯结构，具有约 1, 2-环己二烯反转的障碍。 15 kcal/mol。 1, 2-环戊二烯预计具有 2-5 kcal/mol 的反转势垒，具有手性平衡几何结构。 MCSCF 对平面异质体 (Cf) 的计算表明，由于相关能的差异，开壳层单线态 ('A2) 应低于三线态 (3A2)。四到九元环外星环和双环的半经验（MNDO）计算[3.2。报道了 1]-octa-2,3,6-三烯。
Results of ab initio SCF, MCSCF, and Moller-Plesset calculations on 1, 2-cyclopentadiene and 1, 2-cyclohexadiene are described. 1, 2-Cyclohexadiene is calculated to prefer a chiral allenic structure, with a barrier to inversion of ca. 15 kcal/mol. 1, 2-Cyclopentadiene is predicted to have an inversion barrierof 2-5 kcal/mol, with a chiral equilibrium geometry. MCSCF calculations on planar aliene (Cf) show that theopen-shell singlet ('A2) should be below the triplet (3A2), owing to differences in correlation energy. Semiempirical (MNDO) calculations on four-to nine-membered ring alienes and on bicyclo [3.2. 1]-octa-2, 3, 6-triene are reported.