【作者】 陈海艳；

【导师】 聂永；

【作者基本信息】 济南大学 ， 应用化学， 2009， 硕士

【摘要】 金属硼烷化学是硼烷化学的一个重要分支。从上世纪六十年代以来,硼烷化学一直是一个十分活跃的研究领域,已形成了硼烷、金属硼烷、碳硼烷、金属碳硼烷、主族元素杂硼烷及其金属衍生物等为数众多的研究领域,并展现出许多很有希望的应用前景,如溶剂萃取、催化反应、肿瘤的硼中子俘获治疗、非线性光学材料、液晶、离子选择性电极、阳离子相转移和高能电池的电解质以及主客体化学等。同时,拓扑结构理论、多面体骨架电子对理论等的提出也推动了结构化学的发展,进一步拓宽了结构化学的研究范围。因此,研究这类化合物的合成与结构在理论和实际应用上都是有意义的。论文主要研究了过渡金属配合物[PtCl2（PPh3）2]、[RuCl2（PPh3）3]分别与closo-[B₁₀H₁₀]^2-在不同的溶剂（甲醇、乙醇、叔丁醇等）、不同反应时间、不同的反应方式（回流、溶剂热）下的反应。对反应产物进行了分离和结构表征,并进行了部分反应性研究。本论文主要内容共分四章:第一章介绍了硼烷化学的发展简史和研究现状,综述了闭式（closo）硼烷[B₁₀H₁₀]^2-的反应性,特别关注最新进展及由此衍生的金属高硼烷簇合物的合成与结构。提出本论文的目的及意义。第二章研究了[PtCl2（PPh3）2]与closo-[B₁₀H₁₀]^2-分别在甲醇、叔丁醇及硫代乙酸/二氯甲烷中的回流反应,得到了三个十一顶巢式铂硼烷:[（PPh3）2PtB₁₀H10-9-（OCH3）-11-（H）0.5（OCH3）0.5] （1）,[（PPh3）2PtB₁₀H10-9,10-（H0.7Cl0.3）2] （3）,[（PPh3）2PtB₁₀H11-11-OOCCH3]·CH2Cl2 （4）。还研究了在甲醇中的溶剂热反应得到了一个巢式十一顶双铂硼烷簇合物[（PPh3）2Pt（μ-PPh2）PtB9H6-3,9,11-（OMe）3] （2）,并通过元素分析、红外光谱、核磁共振谱、单晶X-射线衍射进行了表征。结构分析表明,1,3,4这三个铂硼烷簇合物的骨架基本类似,都具有巢式{PtB₁₀}骨架结构,铂原子处于开口的PtB4面上,除了与四个硼原子成键外,还与两个笼外三苯基膦配位。簇合物2具有Pt2B9多面体骨架结构,两个Pt原子位于Pt2B3面上的相邻位置,且由一个PPh2基团桥连,每个Pt原子还分别与三个B原子和一个PPh3配体中的P原子成键。第三章研究了[RuCl2（PPh3）3]和closo-[B₁₀H₁₀]^2-分别在不同溶剂中的反应。其中在乙醇中回流反应得到了阴离子型簇合物[Et4N][（PPh3）RuClB10H8（OEt）2] （5）,并研究了簇合物5的反应性。其中5与二齿配体2,2’-联吡啶（bpy）发生取代反应生成[（bpy）2RuB10H8（OEt）2] （6）。簇合物5、6中一个钌和十个硼原子形成一个闭式的1:2:4:2:2堆积的{RuB10}骨架。钌原子占据闭式骨架结构的顶部,与六个形成船式构型的硼原子相连。对5和6通过红外光谱、核磁共振谱、单晶X-射线衍射进行了表征。在进一步研究过程中意外分离得到了[Et4N][（PPh3）2ClRuB12H12]·CHCl3 （7）,结构分析表明,该簇合物含有分立的钌硼烷阴离子和四乙基铵阳离子,{RuB12H12}是由于合成原料[B₁₀H₁₀]^2-中含有少量closo-[B12H12]2-副产物,后者与[RuCl2（PPh3）3]反应生成的。Ru（II）中心与[B12H12]2-以三个B- H-Ru三中心两电子键结合。第四章对本论文研究的铂、钌配合物与closo-[B₁₀H₁₀]^2-在各种条件下反应得到的金属硼烷产物的合成与结构特点作出总结。更多还原

【Abstract】 Boron cluster chemistry is an interesting and increasingly developing field of study that includes neutral boranes and their anions, metallaboranes, carboranes and metallacarboranes, main group heteroboranes and their metal derivatives. These compounds have provided a lot of interesting potential applications, including solvent extraction, catalysis, boron neutron capture therapy （BNCT） of tumors, nonlinear optics, liquid crystals, ion-selective electrodes, electrolytes for storage batteries and host-guest chemistry. Meanwhile, the topological theory and polyhedral skeletal electron-pair theory propelled the further development of borane chemistry and expanded the scope of structural chemistry. People have been synthesizing large number of boron clusters and modifying their bonding and reaction rules, in the hope of obtaining new boron clusters with special applications.Therefore, it is of interest to continue studying the syntheses and structures of new borane derivatives.This thesis describes the research on metallaborane clusters obtained from the reactions of [PtCl2（PPh3）2] or [RuCl2（PPh3）3] and closo-[B₁₀H₁₀]^2- under different conditions.The four sections of this thesis are as follows:In chapter 1, a general review is given to introduce the development of boron cluster chemistry in particular that of closo-[B₁₀H₁₀]^2-, the structures of the transition metal metallaborane clusters.In chapter 2, the reactions of [PtCl2（PPh3）2] with closo-[B₁₀H₁₀]^2- in refluxing MeOH, tBuOH and CH3COSH/CH2Cl2, respectively, are described. The three eleven-vertex platinaborane products: [（PPh3）2PtB₁₀H10-9-（OCH3）-11-（H）0.5（OCH3）0.5] （1） ,[（PPh3）2PtB₁₀H10-9,10-（H0.7Cl0.3）2] （3）,[（PPh3）2PtB₁₀H11-11-OOCCH3]·CH2Cl2 （4）. The 1,3,4 clusters have nido 11-vertex {PtB₁₀} polyhedral skeleton, in which the Pt atom stay in the open PtB4 face, while connecting with four B atoms and two PPh3 ligands. A diplatinaborane [（PPh3）2Pt（μ-PPh2）PtB9H6-3,9,11-（OMe）3] （2） is obtained from the reaction of [PtCl2（PPh3）2] with closo-[B₁₀H₁₀]^2- in MeOH under solvothermal condition. Compound 2 has a nido 11-vertex {Pt2B9} polyhedral skeleton, in which two Pt atoms stay in adjacent position on the open Pt2B3 face and further bridged by a PPh2 group. Each Pt atom coordinates to three B atoms and a P atom of the PPh3 ligand. Some of these products are characterized by IR, NMR, elemental analysis and single-crystal X-ray analyses.In chapter 3, we studied the reactions of [RuCl2（PPh3）3] and closo-[B₁₀H₁₀]^2- in different solutions. The reaction in refluxing CH3CH2OH affords an anionic ruthenaborane cluster: [Et4N][（PPh3）RuClB10H8（OEt）2] （5）. Compound 5 reacted with 2,2’-bipyridine to afford the ruthenaborane cluster [（bpy）2RuB10H8（OEt）2] （6）. Both 5 and 6 are characterized by IR, NMR and single-crystal X-ray analyses. The clusters 5 and 6 are based on a closo-type 1:2:4:2:2 {RuB10} stack with the metal occuping the unique six-connected apical position and can be considered as having isocloso structures derived from the complete capping of the open face of an arachano geometry to give a completely closed deltaheral cluster. [Et4N][（PPh3）2ClRuB12H12]·CHCl3 （7） was unexpectedly isolated from above the same reaction as a red air-stable solid, in cluster 7 the integrity of the closo-[B12H12]2- is maintained and the Ru（II） center coordinates to two PPh3, a Cl- and three exo-B-H units of the closo-[B12H12]2-, with a distorted octahedral geometry.In chapter 4, the reactions studied using Pt and Ru complexs and closo-[B₁₀H₁₀]^2- under different conditions are concluded as well as the structural characters of the products.更多还原