【作者】 龚磊；

【导师】 夏海平；

【作者基本信息】 厦门大学 ， 高分子化学与物理， 2008， 博士

【摘要】 杂环化学是有机化学中最活跃的研究领域之一,它与生命科学、材料科学等学科均有着十分密切的联系。杂环化合物的研究不仅在理论上有着重要的指导意义,而且在实际应用方面也不断影响着人们的日常生活。随着其研究的快速发展,杂环化合物的杂原子已由O、S、N、P、Si等非金属元素拓展到过渡金属元素。过渡金属种类多、有d、f轨道、多价态、可引入不同官能配体,它们的引入使得杂环化学的分子设计空间得到极大的拓展。过渡金属杂环化合物特殊的分子结构、化学活性、物理性能及潜在的应用前景给化学的多个二级学科和生命与材料科学相关领域的发展带来全新的机遇和挑战。本论文将课题组[5+1]关环合成金属苯双季鏻盐的方法发展为简便的[n+1]关环法,并将该法应用到多类金属杂环化合物的合成中,制备了一系列结构新颖的锇、钌、铱杂五、六元环化合物。也对这些化合物进行了系统的表征,还初步研究了部分化合物的反应性:第一章为绪论,对过渡金属杂环化合物的研究现状、结构特点、合成方法以及潜在的催化性能进行了简单的评述。同时,结合本论文的核心内容,分别介绍了过渡金属杂芳香化合物和分子内配位过渡金属有机化合物（IC化合物）的研究进展。此外,对文章的主要设想与目的也进行了阐述。第二章主要研究基于[5+1]关环法的锇杂环化合物合成。本章分别以C₅有机配体HC≡CCH（OH）CH=CH₂和HC≡CC（CH₃）,（OH）CH=CH₂与锇配合物OsCl₂（PPh₃）₃反应,利用PPh₃对配位炔烃的加成和末端烯烃或炔烃对金属配位的协同反应来完成[5+1]关环,从而发现了合成锇杂环配合物的简便、有效的新方法。首先,合成出两种具有反应活性的金属杂五元环IC配合物OsCl₂（PPh₃）₂(CH=C（PPh₃）CH（OH）CH=CH₂和OsCl₂（PPh₃）₂(CH=C（PPh₃）C（=CH₂）-CH=CH₂,并对它们进行了系统表征;进而,研究了这些活性五元配合物的反应性,合成出多种稳定的锇杂环配合物,其中包括锇苯、锇呋喃、含配位联烯的锇杂IC环化合化物、含锇卡宾的IC环化物、首例锇杂环戊二烯化合物等多元化的产物。第三章主要阐述从锇苯中间体合成锇杂环化合物的方法。探讨了锇苯中间体的反应性,合成出首例稳定的对一金属苯酚、含α,β-不饱和酮的锇杂环IC化合物,锇呋喃,锇杂环戊二烯化合物等化合物,并进行了系统表征和反应机理推测。第四章为金属苯反应性的初步研究。初步考察了本课题组两种代表性金属苯-锇苯和钌苯的三类反应:脱氯反应、与含氮多齿配体的反应、与醛/Lewis酸的金属苯开环反应,制备了多种金属有机配合物和有机化合物,其中包括两类结构新颖的非配位型双金属苯。第五章主要研究基于[4+1]关环法的铱杂环化合物合成。探索了18e配位饱和的铱氢配合物IrHCl（PPh₃）₃与三种类型的炔烃HC≡CCH（OH）C≡CH,C₆H₅C≡CH,C₆H₅CH（OH）C≡CH的反应。这些反应以[4+1]关环法为基础,涉及PPh₃对炔烃的加成、金属氢对炔烃的加成、碳氢活化等多种反应历程,合成了共轭桥联铱氧杂六元环二聚体（即含十个sp²杂化碳桥联的铱二聚体）、铱茚配合物等结构新颖的铱杂五、六元环化合物。此外,还对共轭桥联铱氧杂六元环二聚体的热性能、电化学性能及反应性进行了研究。第六章总结了本论文研究工作的创新性,并对后续的工作进行了展望。更多还原

【Abstract】 Heterocyclic chemistry is one of the most active research fields of organic chemistry, which has close connection with life science and material science. Research into heterocyclic compounds has important guiding significance in theory. And its application research also affect people’s daily life greatly. A wide variety of new heterocyclic compounds, encompassing transition-metal elements as hetero atoms, is now available. Owing to the characteristic of transition-metal, the molecular design space of heterocyclic compounds has expanded significantly. Because of the special structures, chemical activities, physical properties and potential application prospects of transition-metal-containing metallacycles, there exist many new opportunities and challenges to further develop the related fields of chemistry, biology and material science.In this dissertation,convenient [n+1] cyclization reaction was described which was developed from [5+1] cyclization reaction synthesizing metallabenzenes by our group, and applied in the synthesis several novel 5- or 6-membered metallacycles containing osmium, ruthium and iridium. The reactivities of some complexes havealso been studied preliminarily in the research.The dissertation contains six chapters: （1） research progress in metallacycles; （2） synthesis of osmacycles based on [5+1] cyclization reaction; （3） synthesis of several osmacycles based on the reactivity of an osmabenzene intermediate complex; （4） preliminary studies on the reactivity of metallabenzenes; （5） synthesis of iridacycles based on [4+1] cyclization reaction; （6） Innovation and prospect.Chapter 1 reviews the research progress, structural characteristics, synthesis methods and potential catalytic properties of transition-metal-containing metallacycles. According to the main objective of this dissertation, the research progress of transition-metal-containing metallaromatic complexes and intramolecular-coordination metallacycles is also reviewed in this chapter. In addition, the research objectives of this dissertation are presented.Chapter 2 is mainly about synthesis of osmacycles based on [5+1] cyclization reaction.Two active five-membered intramolecular-coordination osmacycles O_SCl₂（PPh₃）₂(CH=C（PPh₃）CH（OH）CH=CH₂ and O_SCl₂（PPh₃）₂(CH=C（PPh₃）-C（=CH₂）CH=CH₂ were synthesized from the reactions of C₅ reagants （HC≡CCH（OH）CH=CH₂ or HC≡CC（CH₃）（OH）CH=CH₂） with an osmium complex O_SCl₂（PPh₃）₃.These cyclometallation process contained the addtion reactions of PPh₃ and the coordinations of the terminal alkyne or alkene groups. During the investigation of the reactivity of O_SCl₂（PPh₃）₂(CH=C（PPh₃）CH（OH）CH=CH₂ and O_SCl₂（PPh₃）₂(CH=C（PPh₃）C（=CH₂）CH=CH2, several stable osmacycles with novel structure, such as osmabenzenes, osmafurans, osmacycles containing intramolecular-coordinated allene, intramolecular-coordination osmacycles containing osmacarbene, an osmacyclopentadiene, were isolated during the investigation of the reactivity of O_SCl₂（PPh₃）₂(CH=C（PPh₃）CH（OH）CH=CH₂ and O_SCl₂（PPh₃）₂-(CH=C（PPh₃）C（=CH₂）CH=CH₂.In addition, some convenient and efficient methods to prepare these osmacycles were developed.In chapter 3, the studies on synthesis of osmacycles from an osmabenzene intermediate complex is discussed. The first p-osmaphenol,several osmacycles containing intramolecular-coordinatedα,β-unsaturated ketone, an osmafuran, an osmacyclopentadiene were synthesized and well characterized. And the plausible mechanisms for the formation of these complexes were also proposed in this chapter.Chapter 4 describes preliminary studies on the reactivity of metallabenzenes. Three kinds of reactions of the representative osmabenzene and ruthenabenzene synthesized by our group, including dechloride reactions, substitution reactions with polydentate nitrogen-containing ligands, and reactions with aldehydes/Lewis acids systems, were investigated. During the investigation, several organometallic complexes and organic compounds, including two none-coordinated bisruthenabenzenes, were obtained.Chapter 5 describes the synthesis of iridacycles based on [4+1] cyclization reaction. In this chapter, three different alkynes, HC≡CCH（OH）C≡CH,C₆H₅C≡CH and C₆H₅CH（OH）C≡CH,reacted respectively with 18e iridium hydride complex IrHCl（PPh₃）₃.These reactions were based on [4+1] cyclization reaction and involved the additions of PPh₃ to the alkyne groups, additions of indium hydride to the alkyne groups or/and C-H activation reactions. Several novel 5- or 6-membered iridacycles, including bimetallic iridium complexes with a bridge of ten sp²-carbon chain and an iridaindene complexes, were synthesized and characterized. Furthermore, the thermal and electrochemical properties as well as the reactivity of the bimetallic iridium complexe with a bridge of ten sp²-carbon chain have also been investigated.In chapter 6, the innovation of the dissertation is concluded and the prospect of this research is presented.更多还原