【作者】 王爱臣；

【导师】 李晓燕； 孙宏建；

【作者基本信息】 山东大学 ， 有机化学， 2009， 博士

【摘要】 第一部分高价态过渡金属膦基卡宾卡拜化合物的合成及反应性能研究20世纪50年代初二茂铁的发现是过渡金属有机化学发展的里程碑。五十多年以来,对过渡金属有机化合物的研究已取得了很大的成就,这类化合物在有机合成、催化等领域的应用,极大地推动了有机化学的发展。目前,过渡金属有机化合物已用于加氢、脱氢、氧化、还原、异构化、羰基化、氢甲酰化、羧基化、聚合等反应。自从1973年E.O.Fischer合成了第一个含有金属碳叁键的金属卡拜化合物以来,金属卡拜化合物的合成和反应性能一直是金属有机化学中的前沿研究领域之一。由于这类化合物有各种奇特的反应性能,在有机合成中,尤其是在维生素,多肽,抗癌药物和天然产物的合成,和作为烯烃,炔烃聚合催化剂方面显示出其独特的优越性和广阔的应用前景。但是由于金属卡拜化合物的合成和反应复杂,至今卡拜化合物的化学发展并不完善。在卡拜化合物中,与卡拜碳上相连的基团的性质强烈影响金属—碳三重键的强度及其反应活性。膦基卡拜化合物作为一种特殊的卡拜化合物（M≡C—PR₃（?）M=C=PR₃）,可视为双金属取代的膦叶立德,将是一类具有特殊化学反应性能的金属有机化合物,在有机合成和催化反应中具有潜在的应用前景。但到目前为止,有关高价态过渡金属（d⁰）膦基卡拜化合物的研究报道非常少见。因此本论文部分主要研究了高价态过渡金属（d⁰）膦基卡宾卡拜化合物的合成及反应性质,具体研究内容如下:1.高价态过渡金属钽叶立德加合物的合成过渡金属叶立德化合物的合成及其性质反应越来越引起化学家的极大兴趣,因为此类化合物是某些催化反应的重要中间体,也可以催化一些新的反应。例如金属叶立德加合物广泛应用于有机合成,也可以作为合成高价态过渡金属膦基卡宾卡拜化合物的前躯体。本课题利用（环戊二烯基）四氯化钽和（五甲基环戊二烯基）四氯化钽为原料,与膦叶立德H₂C=P（NEt₂）₃ 1:1反应成功合成分离出钽（Ⅴ）膦叶立德加合物trans-CpTaCl₄[H₂C-P（NEt₂）₃]（4）和trans-Cp^*TaCl₄[H₂C-P（NEt₂）₃]（5）。化合物5为前躯体继续与叶立德反应可以得到了一种金属钽作为阴离子的离子型化合物[H₃C-P（NEt₂）₃][Cp^*TaCl₅]（7）。2.高价态金属钛膦基卡宾化合物的合成及性质反应以（五甲基环戊二烯基）三氯化钛（3）为原料,与H₂C=PPh₃通过叶立德转化反应,成功得到金属钛（Ⅳ）的膦基卡宾化合物Cp^*TiCl₂（=CH-PPh₃）（8）,由于金属钛原子半径小及PPh₃的空间位阻导致此化合物通过过量叶立德,LiN（SiMe₃）₂或NaN（SiMe₃）₂作用并不能生成卡拜化合物。化合物（8）与小分子CO作用,发生还原聚合反应生成双核[Cp^*Ti（μ-Cl）Cl]₂（9）及三核钛[Cp^*Ti（μ-Cl）Cl]₃（10）的簇合物。3.高价态金属钽膦基卡拜化合物的合成及性质反应以（环戊二烯基）四氯化钽为原料,与七当量的H₂C=PPh₃通过叶立德转化反应,得到高价态金属钽膦基卡拜化合物CpTa（≡C—PPh₃）（=CH—PPh₃）₂（11）。为了提高卡拜化合物的产率和稳定性,我们在金属钽配合物（1）上引入供电子基团（苯硫酚）,采用“一锅煮”法与叶立德发生转化反应,同样也可以得到金属钽的膦基卡拜化合物（12-19）。以（五甲基环戊二烯基）四氯化钽为原料,和叶立德H₂C=PPh₃ 1:1反应生成加合物trans-Cp^*TaCl₄[H₂C-PPh₃]（6）,然后在不同有机碱H₂C=PPh₃,（Me₃Si）₂N^-,和吡啶及不同当量的作用下,化合物6可以选择性脱除氢,得到高价态膦基卡拜化合物Cp^*Ta（≡C—PPh₃）（=CH—PPh₃）Cl（21）和双亚甲基配位的化合物（20）。对于化合物11,详细研究了其与小分子加成反应、炔烃复分解反应以及通过Wittig反应制备高价态过渡金属丙二烯基卡宾化合物。化合物11与小分子加成反应现象明显但没有分离提纯出产物,与炔烃的复分解反应受到炔烃极性和空间效应的影响较大,而发生Wittig反应效果明显,初步推断反应停留在中间体（24）一步,其尚需进一步表征。本课题对实验过程中获得的新化合物采用¹H,¹³C和³¹PNMR等手段进行了表征,并对其中获得单晶的化合物进一步采用X-ray衍射分析证实结构。更多还原

【Abstract】 The discovery of ferrocene in the 1950s is a milestone in the development of organometallic Chemistry.During these 50 years,the research of transition metal organic compounds has made great achievements.The application of these compounds in organic synthesis and catalytic fields has promoted the development of organic chemistry greatly. Currently,transition metal organic compounds have been used for hydrogenation, dehydrogenation,oxidation,reduction,isomerization,carbonylation,hydroformylation, carboxylation,polymerization reaction.The synthesis and properties of metal-carbyne complexes is always a hot topic in the research field of organometallic chemistry since the first synthesis of transition metal complexes with a formal metal-carbon triple bond reported by E.O.Fischer et al.in 1973. Since these compounds have various particular reactions in organic synthesis,especially in vitamins,peptides,synthesis of anti-cancer drugs and natural products,and as olefins, alkyne polymerization catalysts demonstrated its unique advantages and broad application prospects.Due to the difficulty synthesis of the metal-carbyne complexes and their complicated reaction,the development of metal-carbyne is not perfect until now.The functional group linked to carbyne carbon has a strong effect on the reactivity and strength of metal-carbon triple bond.The phosphorous ylide carbyne complexes as a kind of special carbyne complexes（M≡C—PR₃??M = C =PR₃ ） could be regarded as a double-metal substituted complex of phosphorous ylide and they have special chemical properties with application potential in organic synthesis and catalysis.Very few examples of high-valent transition metal phosphonio methylidyne complexes with d⁰ electron configuration are known so far.This part of dissertation mainly concerns the synthesis and properties of high-valent transition metal phosphonio methylidene/yne complexes with d⁰ electron configuration.The main contents are shown as follows:1.Formation of high-valent transiton metal tantalum ylide adduct complexesThe synthesis and chemistry of transition-metal phosphonium ylide complexes have been extensively investigated.Interet in this class of organometallic complexes arises principally because these complexes may be important intermediates in catalytic reactions and are considered potential catalysts for new processes.Additionally,however, ylide complexes are beginning to be exploited in stoichiometric organometallic chemistry as versatile substrates for further synthetic manipulation:essentially the same reason phosphonium ylides are used so extensively in organic synthesis,and ylide complexes can be as a precursor for the formation of phosphonio methylidyne complexes of trasition metal with d⁰ electron configurations.Herein we employed（Et₂N）₃P=CH₂ ylide and studied their reaction with cyclopentadienyl（Cp） tantulum（V） tetrachloride and pentamethylcyclopendienyl（Cp*） tantulum（V） tetrachloride,and finally two ylide adduct complexes trans-CpTaCl₄[H₂C-P（NEt₂）₃]（4） and trans-Cp*TaCl₄[H₂C-P（NEt₂）₃] （5） and an ionic complex[H₃C-P（NEt₂）₃][Cp*TaCl₅]（7） were obtained.2.The simply synthesis and property of high-valent transition titanium phosphonio methylideneA simple synthesis ofα-phosphonio（methylidene） complexes of titanium [Cp*TiCl₂（=CH-PPh₃）]（8） was obtained from transylidation reactions of pentamethylcyclopentadienyl titanium trichloride Cp*TiCl₃ with 2 equiv of Ph₃P=CH₂. Because of the smaller atomic radius of titanium and the bigger steric hindrance of Cp* and PPh₃,more than two molecular of ylide,LiN（SiMe₃）₂ and NaN（SiMe₃）₂ were used to depronated another phosphonium chloride from complex 8 in order to obtain phosphonio-methylidyne or ylide-bridged metallacycle complex,but failed.These unexpected dinuclear[Cp*Ti（μ-Cl）Cl]₂（9） and trinuclear[Cp*Ti（μ-Cl）Cl]₃（10） titanium（Ⅲ） complexes were formed through reduction reaction of complex 8 with CO.3.The synthesis and properties of high-valent transition tantulum phosphonio methylidyneTheα-phosphonio（methylidyne） complexes of tantalum CpTa（≡C—PPh₃）（=CH-PPh₃） ₂（11） was obtained from transylidation reactions of cyclopentadienyl tantalum tetrachloride CpTaCl₄（1） with 7 equiv of Ph₃P=CH₂.In order to improve the yield and the stablity of the carbyne complexes,thiophenol group was introduced to connect to the tantalum center of compound 1.And "one pot" ylide transylidation reactions were carried out and the carbyne complexes（12-19） were also obtained. Cp*TaCl₄（CH₂=PPh₃）（6） can be got from the reaction of Cp*TaCl₄ with one equiv of Ph₃P=CH₂,and regioselective deprotoned by the different bases Ph₃P=CH₂,（Me₃Si）₂N^-and pyridine to giveα-phosphonio（methylidyne） complexes of tantalum（21） and complex（20） coordinated by two methylene groups.The properties of carbye compound 11 has also been studied.For example,the addition reaction with small molecular,the metathetical reaction with alkynes and Wittig reaction to prepare high-valent transtion-metal allenylidene complexes.The reactions with small molecular,the main products maybe further proved;the metathetical reaction was effect by the polarity and spatial property of alkynes;and the Wittig reaction were carried out to stand the intermediate（24）.All of the new complexes are characterized by IR,¹H,¹³C and ³¹p NMR.Structrures of some single crystals have been confirmed by X-ray diffraction techniques.更多还原