McKay Scott E, Lashlee Robert W, Holthouse Bryce A, Kiprof Paul
Department of Chemistry and Physics, Central Missouri State University, Warrensburg, MO, USA.
J Mol Graph Model. 2006 Dec;25(4):543-8. doi: 10.1016/j.jmgm.2006.04.006. Epub 2006 Apr 30.
Calculations of several thiacyclooctatetraenophanes predicted, as part of their overall geometry, substantial flattening of the cyclooctatetraene (COT) structures relative to the tub conformation generally associated with the COT molecule. The COT structures were approximately parallel to each other and the interplanar distances were predicted to be within 2.787-2.803 angstrom at the DFT/UB3YLP level of calculation. DFT/UB3LYP optimized geometries afforded significant delocalization of the COT structures in each of the thiacyclooctatetraenophanes. Hartree-Fock (HF) methods and the semi-empirical Austin Model 1 (AM1) method deviated significantly from the DFT/UB3LYP optimized geometries. Cyclooctatetraenes can undergo reversible sizing by oxidation and reduction reactions to form the aromatic dication and aromatic dianion, respectively, which could then be used to prepare molecular backbones for polymeric organometallic molecular wires. The number of bridges and the introduction of the sulfur atom have been investigated to provide disparate synthetic routes.
对几种硫杂环辛四烯并环戊二烯的计算预测，作为其整体几何结构的一部分，环辛四烯（COT）结构相对于通常与COT分子相关的 tub 构象会有显著的扁平化。COT结构彼此大致平行，在DFT/UB3YLP计算水平下，平面间距预计在2.787 - 2.803埃范围内。DFT/UB3LYP优化的几何结构在每种硫杂环辛四烯并环戊二烯中都使COT结构有显著的离域。哈特里 - 福克（HF）方法和半经验的奥斯汀模型1（AM1）方法与DFT/UB3LYP优化的几何结构有显著偏差。环辛四烯可通过氧化和还原反应分别进行可逆的尺寸变化，形成芳香族二价阳离子和芳香族二价阴离子，然后可用于制备聚合物有机金属分子线的分子骨架。已对桥的数量和硫原子的引入进行了研究，以提供不同的合成路线。
