物理化学学报 >> 2009, Vol. 25 >> Issue (09): 1847-1852.doi: 10.3866/PKU.WHXB20090912

研究论文 上一篇    下一篇

包含平面四配位和五配位碳原子的特殊硼碳化合物

梁锦霞, 贾文红, 张聪杰, 曹泽星   

  1. 陕西师范大学化学与材料科学学院, 陕西省大分子科学重点实验室, 西安 710062|厦门大学化学系, 固体表面物理化学国家重点实验室, 福建 厦门 361005
  • 收稿日期:2009-04-15 修回日期:2009-05-20 发布日期:2009-09-03
  • 通讯作者: 张聪杰 E-mail:zcjwh@snnu.edu.cn

Unusual Boron-Carbon Compounds Containing Planar Tetracoordinate and Pentacoordinate Carbons

LIANG Jing-Xia, JIA Wen-Hong, ZHANG Cong-Jie, CAO Ze-Xing   

  1. Key Laboratory of Macromolecular Science of Shaanxi Province, School of Chemistry &Materials Science, Shaanxi Normal University, Xi'an 710062, P. R. China|State Key Laboratory of Physical Chemistry of Solid Surfaces, Department of Chemistry| Xiamen University, Xiamen 361005, Fujian Province, P. R. China
  • Received:2009-04-15 Revised:2009-05-20 Published:2009-09-03
  • Contact: ZHANG Cong-Jie E-mail:zcjwh@snnu.edu.cn

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摘要：

采用密度泛函理论(DFT), 在B3LYP/6-311+G**水平上, 研究了三类包含平面四配位碳原子(ptC)和平面五配位碳原子(ppC)的硼碳化合物. 这三类新型化合物是由C3B2H4(包含ptC)、CB4H2(包含ptC)和CB5H2(包含ppC)三种稳定结构和—CHCH—单元连接起来而得到的. 在理论上探讨了这些新型的硼碳化合物的成键特征, 光谱性质以及芳香性. 研究结果表明: 包含ptC和ppC原子的能量最低的结构, 在不受对称面限制的条件下, 具有C2v对称性的顺式立体构型比具有反式平面构型的化合物稳定. 计算的核独立化学位移(NICS)显示, 这些新型化合物的三元环中心有强的芳香性. 计算最稳定硼碳化合物的ptC和ppC原子的Wiberg键指数(WBIs)表明ptC和ppC的成键遵循八隅规则.

关键词: 密度泛函理论, 平面四配位碳, 平面五配位碳, 芳香性

Abstract:

Unusual boron-carbon compounds containing planar tetracoordinate carbon (ptC) and planar pentacoordinate carbon (ppC) were investigated using density functional theory (DFT) at B3LYP/6-311+G**level. These novel compounds are generally assembled with three types of stable structural units C3B2H4 with ptC, CB4H2 with ptC, and CB5H2 with ppC as well as linking elements —CHCH—. On the basis of calculation results the bonding features, spectroscopic properties, and the aromaticities of these novel boron-carbon compounds were discussed. Results show that as for the lowest-energy compounds contained ptC and ppC without being limited by symmetrical planes, stereo cis-structures of C2v symmetry are more stable than the corresponding planar trans-structures. Calculated nucleus- independent chemical shift (NICS) values show that the aromaticity of the center of the three-membered rings is the strongest. The total Wiberg bond indices (WBIs) of the ptC and ppC atoms of the most stable structures of the boron-carbon compounds indicate that the ptC and ppC obey the octal rule.

Key words: Density functional theory, Planar tetracoordinate carbon, Planar pentacoordinate carbon, Aromaticity

MSC2000: 

  • O641