The quinones of bicyclo[3.1.0]hexatriene: A computational study of their chemistry and thermochemistry

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• 作者：Aimé ; Kayembe^a ; Errol Lewars^a ; ^{elewars@trentu.ca} ; Joel F. Liebman^b ; ^{jliebman@umbc.edu}
• 关键词：Quinones ; Quantum chemical calculations ; Enthalpy of formation ; Classical and nonclassical structures ; m-Benzyne ; Crossbonds ; Shortbond isomer ; Longbond isomer
• 刊名：Journal of Chemical Thermodynamics
• 出版年：2012
• 期刊代码：123_00219614
• 类别：ch
• 出版时间：September, 2012
• 卷：52
• 期：Complete
• 页码：43-56
• 文件大小：710 K

摘要

Quinones of bicyclo[3.1.0]hexa-1,3,5-triene were examined computationally. The six compounds considered were the five possible classical and one non-classical quinone: bicyclo[3.1.0]hexa-1(6),4-diene-2,3-dione (and its monocyclic isomer with a long trans-annular bond), bicyclo[3.1.0]hexa-1(5),3-diene-2,6-dione, bicyclo[3.1.0]hexa-1,4-diene-3,6-dione (and its monocyclic isomer with a long trans-annular bond), and bicyclo[3.1.0]hexa-1(5),4-diene-2,4-dione-3,6-diyl, a non-classical (non-Kekul茅) zwitterion. The two long trans-annular bond structures are akin to that found for m-benzyne. Geometries were calculated (BLYP/6-31G^{鈭?/sup>, CASSCF(2,2)/6-31G鈭?/sup>, MP2/6-31G鈭?/sup>) and electronic structural inferences were made from the geometries. Also calculated were relative energies and heats of formation (CBS-QB3), singlet and triplet energies (BLYP/6-31G鈭?/sup>), and ionization energies and electron affinities (HF/6-311+G鈭椻垪//BLYP/6-31G鈭?/sup>). The NICS(1) calculations were performed as a probe of the aromaticity of the diverse quinones.}