Minyaev Ruslan M, Gribanova Tatyana N, Minkin Vladimir I, Starikov Andrey G, Hoffmann Roald
Institute of Physical and Organic Chemistry at Rostov State University, Southern Research Center of Russian Academy of Sciences, Rostov-on-Don, Russian Federation.
J Org Chem. 2005 Aug 19;70(17):6693-704. doi: 10.1021/jo050651j.
Using previously proposed C(BH)2(CH)2 (16, 17) and C(CH)2B2 (22) systems with a central planar tetracoordinate carbon (ptC) atom linking two three-membered rings as building blocks, a series of stable structures containing two and three ptC centers within a molecule have been designed and computationally studied with the DFT (B3LYP/6-311+G) method. Inclusion of a carbon atom ligated with pi-accepting and sigma-donating boron centers into at least one aromatic ring is critical for stabilization of a planar structure. A square pyramidal configuration at tetracoordinate carbon may be achieved in appropriately strained molecules such as [3.3.3.3]tetraborafenestrane 45 and others by surrounding the carbon with boron-centered ligands.
使用先前提出的以连接两个三元环的中心平面四配位碳（ptC）原子为结构单元的C(BH)2(CH)2（16, 17）和C(CH)2B2（22）体系，通过密度泛函理论（DFT，B3LYP/6 - 311 + G方法）设计并计算研究了一系列分子内含有两个和三个ptC中心的稳定结构。将与π-吸电子和σ-给电子硼中心相连的碳原子纳入至少一个芳环对于平面结构的稳定至关重要。在诸如[3.3.3.3]四硼方烷45等适当应变的分子中，通过以硼为中心的配体围绕碳，可以实现四配位碳的四方锥构型。
