基于σ#960;能量分解的平面多配位原子稳定性及配位性的研究

项目名称： 基于σ#960;能量分解的平面多配位原子稳定性及配位性的研究

项目编号： No.20802093

项目类型： 青年科学基金项目

立项/批准年度： 2009

项目学科： 化学工业

项目作者： 罗琼

作者单位： 中南大学

项目金额： 18万元

中文摘要： 本研究采用热力学与动力学方法相结合探索平面多配位碳原子稳定存在的一般性规律和配位性能。在此基础上，我们得到：（1）优化出新的稳定平面多配位原子环，尤其是D5h简单平面五配位C原子环CBe5和CBe54-。并开展了CBe54-的化学性质的研究，发现含平面五配位C原子的CBe5(Be)2-是势能面上的最低点，为实验合成平面五配位C原子提供了简单模型。（2）为了扩大B配位环在构造平面多配位原子的应用范围，探索了B五元环构造平面五配位B的可能性，研究了B6势能面和B9, B9- 和 B9+的势能面，发现B9在势能面上的最稳定点是一个D7h 的双星结构。（3）研究了铝作为+1价配体形成的原子簇Al3X (X=B、C、N) 的结构和性质。与其它分子，包括其双分子相互作用时，表现出很好的结构整体性，显现无论在分子结构或化学性质，分别类似于第六、七族和惰性气体主族元素。以上研究丰富已有化合物的类型，深化对C原子及其它原子的化学成键性质和能力,特别是对各种平面多配位原子环配位的金属配合物中化学键性质的认识,丰富碳化学和配位化学的知识

中文关键词： 平面多配位原子；金属配合物； 计算量子化学；

英文摘要： The stability rule and coordination ability of multicoordinate planar carbon have been investigated by using the thermodynamics and dynamics methods. The following results are obtained:(1) The smallest molecules up to date containing a D5h pentacoordinate planar carbon (PPC) atom, CBe5 and CBe54?, are predicted by means of ab initio calculations.The calculations show that σccepting metals, such as Li+, Be2+, and Al3+, bonding to edges of the D5h CBe54- anion can stabilize these ppC-containing molecules with ppC CBe5 skeleton. (2) The interconversions between isomers with the same spin multiplicity of neutral B6 and charged B6- and B6+ clusters have been investigated. The stability of each isomer of B6 (singlet and triplet states), B6- (doublet state) and B6+ (doublet state) were analyzed from both thermodynamic and dynamic viewpoints. As well as, 28 isomers of B9 (1-10), B9+ (1+-8+) and B9- (1- - 10-) clusters, including five isomers reported previously. The results suggest that B9, B9+ and B9- clusters have their global minima to be the D7h-symmetry heptagonal bipyramid structure, the Cs-symmetry wheel-shaped structure and the D8h-symmetry planar wheel-shaped structure, respectively. (3) Different from the usual salt formed by interaction between Al (Ⅲ and nonmetal elements, it is researched that Al (Ⅰ can be used as the ligand to form cluster Al3X (X = B、C、N) which can be used to construct supermolecules and new materials. The above research results add the type of compounds and give a light to the bond properties and abilities of carbon and other elements, especially for the bond characters of the metal-complexes coordinated by multicoordinate planar atoms.

英文关键词： multicoordinate planar atom; metal coordinate complexe; computational quantum chemistry；