【作者】 吴芳辉；

【导师】 陆路德； 汪信；

【作者基本信息】 南京理工大学 ， 化学工程与技术， 2010， 博士

【摘要】 富电子硫配位环境下的金属钌配合物因为与生物和工业催化过程有关而引起了广泛的研究兴趣,因此本论文设计与制备了一系列不同构型和特征的双齿或多齿硫配体,对结构新型且具有潜在催化性能的有机钌化合物进行合成与表征,并研究了它们的反应特性、晶体结构以及光电化学性能。采用溶液法合成了11种新型的二硫代羧酸配位环境下的单核有机钌化合物（1-11）并归纳总结了合成历程和机理。用单晶X射线衍射仪测定了部分化合物的晶体结构,结果表明,这些化合物中钌原子都采取准八面体构型,而且二硫代羧酸配体均以小咬角与中心钌原子配位。为了进一步探讨二价钌金属中心的反应活性,采用动力学电子吸收光谱研究了强氧化剂（NH₃）₄Ce（NO₃）₆氧化化合物（4）的反应过程。不同化合物的电化学性质研究表明三价态的钌中心原子与σ给体的磷配体以及富电子的含硫配体结合得较紧密。设计合成了五种含多（巯基咪唑）硼配体的具有潜在生物活性和催化性能的有机钌化合物（12-16）,并通过红外光谱、核磁共振氢谱以及元素分析等手段对它们进行了表征。分析化合物（12、13和15）的晶体结构表明,配体与钌配位时有两种配位模式,而采取双齿或三齿配位方式主要决定于钌化合物原料中其它共配体的特征。化合物（12、13和15）中都形成了含悬挂氢的B-H…Ru键,并且总体上为扭曲的八面体构型,表明多（巯基咪唑）硼配体具有较高的反应活性。最后用密度泛函B3LYP方法研究了其中两个化合物（12和13）的优化几何构型、原子电荷分布以及振动频率,并与相应的实验结果进行了比对。采用二茂铁基Lawesson试剂（[FcP（S）（μ-S）]₂）与不同的钌化合物原料在THF溶剂中反应获得三种新型的化合物(17·CH₂Cl₂,18和19·CH₂Cl₂·³/₄C₆H₁₄)并进行了系统的表征。荧光测试结果表明这些化合物具有较弱的荧光性质,而电化学性质的实验则验证了这些化合物的循环伏安曲线与其它含二茂铁基二硫代膦酸根配体的化合物相似。此外还首次报道了一种二异丙基二硫代膦酸钌化合物（20）的晶体结构特征。MoO₂（S₂CNMe₂）₂与RuCl₃·xH₂O在丙酮溶液中加热回流生成一种含二硫代氨基羧酸基团和多钼酸根阴离子的双核钌化合物（21·2CH₃COCH₃）,其中阳离子部分[Ru₂（S₂CNMe₂）₃（μ₃-S₂CNMe₂）₂]⁺基团可以看作是[Ru（S₂CNMe₂）₃]与cis-[Ru（S₂CNMe₂）₂]⁺结合而成,而Lindqvist型阴离[Mo₆O₁₉]^2-恰好位于两个阳离子的倒转中心处。结合红外光谱、磁矩实验和元素分析对化合物（21）加以表征,并研究了其电化学性质。另外还报道了一个新型的含芳香环的单核钌化合物（22）的合成与结构。由[Cp*Ir{N（Ph₂PS）₂}C1]与NaN3在丙酮溶液中反应很容易将活性氯原子取代而得到化合物（23）,采用单晶X-射线衍射仪分析了该化合物的晶体结构并进行了必要的表征。更多还原

【Abstract】 In recent years there has been an increased interest in ruthenium complexes with sulfur donor ligands for their importance in the field of biological and industrial catalysis process. So we synthesized a series of novel and potential catalytic activity ruthenium complexes containing bidentate or tridentate thiolate ligands and detected their crystal structures. Moreover, reactivity along with spectroscopic and electrochemical properties has also been investigated in detail.Eleven mononuclear ruthenium compounds （1-11） sulfur-donor coordinate environment have been synthesized in this thesis. Then we have summarized the synthesis course and the mechanism for every reaction. The crystal structures of complexes have been determined by single-crystal X-ray diffraction. The ruthenium atom in each of the above complexes adopts a pseudo-octahedral geometry and the 1,1’-dithiolate ligands bind to ruthenium with bite S-Ru-S angles. With the aim of identifying reduction properties of low valence Ru（Ⅱ） center, the kinetic electronic absorption spectrum of reaction between complex 4 with strong oxidant （NH₃）₂Ce（NO₃）₆ was investigated. Electrochemical properties suggest that the ruthenium （Ⅲ） state in these complexes is well stabilized by the combination of of-donor phosphine and electron-rich sulfur ligandsFive novel and potential catalytic activity ruthenium compounds （12-16） containing poly（mercaptoimidazolyl）borate ligands were synthesized and characterized with elemental analysis, IR, NMR and X-ray crystallography. Crystal structure analysis of （12,13 and 15） confirmed that poly（mercaptoimidazolyl）borate ligand can provide a bidentate or tridentate facial coordination mode to form an overall distorted octahedral geometry. Coordination behavior of ligand depends on the properties of coligands. We have shown that poly（mercaptoimidazolyl）borate ligand is a very powerful ligand for ruthenium moieties through remarkably robust B-H…Ru agnostic interaction. Density Functional Theory （DFT） method calculations of the optimized structure, atomic charge distributions and vibrational frequencies for two compounds （12 and 13） were studied and compared with their corresponding experimental results.Treatment of [FcP（S）（u-S）]2 （Ferrocenyl Lawesson’s Reagent） with different ruthenium materials in THF afforded three new complexes (17·CH₂Cl₂,18 and 19·CH₂Cl₂·³/₄C₆H₁₄). These compounds have been characterized by the infrared, UV-Vis, NMR spectroscopies and X-ray crystallography. Three compounds in CH₂Cl₂ solution can emit weak fluorescent due to poor quantum yields. Cyclic voltammogram of three heterobimetallic trinuclear compounds were semblable with other compounds containing ferrocenyldithiophosphonic ligand. Moreover, a novel ruthenium phosphorodithioate complex （20） containing M-S-S bond was synthesized and characterized firstly by X ray diffraction.Reaction of MoO₂（S₂CNMe₂）₂ with RuCl₃·xH2_O in acetone at reflux afforded a dinuclear ruthenium compound （21·2CH₃COCH₃） which was characterized by X-ray diffraction to show ruthenium-dithiocarbamate species as cation and hexamolybdate as counter anion. The [Ru₂（S₂CNMe₂）₃（μ₃-S₂CNMe₂）₂]⁺ cation may be considered as a combination of [Ru（S₂CNMe₂）₃] with a cis-[Ru（S₂CNMe₂）₂]⁺ species, and the Lindqvist anion [Mo₆O₁₉]^2- is located on an inversion center of two cations. Spectroscopic properties along with the electrochemistry of compound 21-2CH3COCH3 are reported. Furthermore, a mononuclear ruthenium complex （22） with arene ligands has been synthesized and structurally characterized.At the end of thesis, we report the synthesis and crystal structure of a Cp*Ir halfsandwich complex （23） containing azido and bis（diphenylthiophosphoryl）amide ligands.更多还原