金属羰基化合物与富烯以及五元杂环取代的环戊二烯的反应研究

河北师范大学硕士学位论文金属羰基化合物与富烯以及五元杂环取代的环戊二烯的反应研究姓名：刘晓焕申请学位级别：硕士专业：有机化学指导教师：林进20081008摘要双核金属络合物是当前金属有机化学的研究热点之一，由于两个金属中心可以协同作用，从而显示出较高的反应活性和催化性能。

对这类化合物的深入研究，不仅丰富和发展金属有机化学理论，还有助于为新型催化反应提供催化剂及反应模型，具有潜在的应用前景。

本论文研究了富烯以及五元杂环取代的环戊二烯与羰基化合物的反应，得到了12种新型的茂金属羰基配合物，部分产物的结构已由X-射线衍射分析测定，并对它们的晶体结构进行了讨论。

主要研究内容如下：设计合成了6种五元杂环取代的环戊二烯配体，并首次将这类配体用于与金属羰基化合物的反应，分离得到了8种新型的茂金属羰基配合物[(η5-C5Me4C4H3S)M(CO)(µ-CO)]2 [M=Ru (6), M=Mo (7)]、[(η5-C5H4)CR1R2(C4H3S)Ru (CO)2]2 [R1, R2=CH3(8), R1=CH3, R2=C2H5(9), R1, R2=(CH2)5(10), R1, R2=C2H5(11)], [(η5-C5Me4(2-CH3C4H2O))Ru(CO)(µ-CO)]2(13)和[(η5-C5Me4(2-CH3C4H2O))Fe(CO) (µ-CO)]2(14)，用红外光谱、核磁共振氢谱以及元素分析对其组成与结构进行了表征，并通过X-射线衍射分析测定了配合物6、8、10、11和13的晶体结构。

晶体结构表明：6、8、10和13具有相似的分子结构，分子中的两个茂环呈反式配位，含有两个桥羰基和端羰基；配合物11只含有四个端羰基，而没有桥羰基，并且在这些配合物中，它拥有最长的Ru-Ru键长。

分子中的Ru-Ru键长随着茂环上取代基空间位阻的变化而变化，空间位阻越大，分子中的Ru-Ru键长越长，反之，则变小。

配体中的五元杂环呋喃或噻吩没能与金属配位成键，只是作为环戊二烯的一种取代基的形式存在，这可能是由于呋喃和噻吩的孤电子对参与了环状芳香体系的形成，因此孤电子对难于参与与金属的配位。

研究了富烯配体C5H4CR1R2 [R1, R2=CH3 (15), R1, R2=C2H5 (16)]与Ru3(CO)12的反应性，分离得到了富烯桥连的Ru-Ru键配合物(η3:η5-C5H4C(CH2)2)Ru2(CO)5(18)和(η3:η5-C5H4C(CHCH2)(C2H5))Ru2(CO)5(19)，晶体结构显示：分子中的环戊二烯以η5的形式与一个Ru原子配位，离域的烯丙基以η3的形式与另一个Ru原子进行了配位，说明了富烯分子中的环外双键在反应过程中发生了迁移，新形成的双键发生离域，并与钌原子进行了配位。

同时，研究了6, 6-四亚甲基富烯配体C5H4C(CH2)4与Ru3(CO)12的反应，得到了以η5模式配位的配合物(η5-C5H4C5H7)2Ru2(CO)2(µ-CO)2 (20)和以η1:η5模式配位的富烯桥连Ru-Ru键配合物(η1:η5-C5H4C5H8)Ru2(CO)6 (21)，通过红外光谱、核磁共振III氢谱以及元素分析确定了21为富烯桥连的Ru-Ru键配合物，富烯分子中的一个环外双键和两个环内双键以η1:η5的配位模式与Ru原子配位。

用X-射线单晶衍射测定了20的晶体结构，晶体结构表明，6, 6-四亚甲基富烯在此反应过程中发生了环外双键的异构化，但该双键并没有与金属配位。

以上结果说明，富烯与金属羰基化合物反应时，可以以不同的配位模式与金属成键，产物结构具有多样性。

不同的配位模式对分子中Ru-Ru键长也有影响，以η3:η5和η1:η5模式配位的富烯桥连配合物比只以η5模式配位的非桥连配合物的Ru-Ru键要长，这可能是因为碳桥的存在，阻碍了两个Ru原子之间更进一步的靠近，使得配合物的Ru-Ru键变长。

关键词：五元杂环富烯环戊二烯基金属羰基化合物异构化IVAbstractIncreasing attention has been paid to dinuclear metal complexes, due to the significant cooperative effect of both metal centers on their reactivity and catalytic applications. Intensive study of these complexes will help to provide new catalysts with potential application prospects and expand organometallic chemical theory. In this dissertation, reactions of fulvenes and five-heterocyclic substituted cyclopentadienes with carbonyl complexes gave 12 corresponding dinuclear metal carbonyl complexes.8 complexes of them were characterized by X-ray diffraction and their structures were also discussed. The main results are listed as following:In this dissertation, 6 five-heterocyclic substituted cyclopentadienyl ligands were designed and synthesized. Reactions of these ligands with metal carbonyl complexes in refluxing xylene gave the corresponding dinuclear metal carbonyl complexes [(η5-C5Me4C4H3S)M(CO)(µ-CO)]2 [M=Ru (6), M=Mo (7)], [(η5-C5H4)CR1R2(C4H3S)Ru (CO)2]2 [R1, R2=CH3(8), R1=CH3, R2=C2H5(9), R1, R2=(CH2)5(10), R1, R2=C2H5(11)], [(η5-C5Me4(2-CH3C4H2O))Ru(CO)(µ-CO)]2 (13) and [(η5-C5Me4(2-CH3C4H2O))Fe(CO) (µ-CO)]2 (14) which have been characterized by IR spectra, 1H NMR, and elemental analysis, and the molecular structures of the complexes 6, 8, 10, 11 and 13 were determined by X-ray diffraction. The structures of the complexes 6, 8, 10 and 13 are similar. They have two types of carbonyl ligands, namely terminal and bridging, in their molecular structures.However, the complex 11 has only four terminal carbonyls without bridging carbonyls, which has a much longer Ru-Ru bond distance than those in the complexes 6, 8, 10 and 13. The steric effects of the substituents had influence on the molecular structures, especially on the Ru-Ru bond distances. The Ru-Ru bond distance increases with the increasing of the steric effect of the substituent, on the contrary, the smaller. The five-heterocyclic furan or thiophene in these ligands did not coordinate with the metal centers. This is mainly attributable to the lone pair electrons in the furan and thiophene, which may be involved in the formation of aromatic systems.Reactions of fulvene ligands C5H4CR1R2 [R1, R2=CH3(15), R1, R2=C2H5(16)] with Ru3(CO)12 were studied respectively, the corresponding fulvene-bridged complexesV(η3:η5-C5H4C(CH2)2)Ru2(CO)5(18) and (η3:η5-C5H4C(CHCH2)(C2H5))Ru2(CO)5(19) were obtained which contain Ru-Ru bond. One Ru atom is coordinated with cyclopentadienyl ligand in η5 manner, the other Ru atom is coordinated with allyl group in η3 manner. It illustrates fulvenes undergo double bond isomerization, which coordinate with the Ru atom in reactions. At the same time, the 6, 6-tetramethylenefulvene was reacted with Ru3(CO)12 in refluxing xylene to give the new dinuclear complexes (η5-C5H4C5H7)2Ru2(CO)2(µ-CO)2 (20) and (η1:η5-C5H8C5H4)Ru2(CO)6(21). By IR spectra, 1H NMR, and elemental analysis, complex 21 has been identified as the fulvene-bridged diruthenium complex and its structure reveals that an exocyclic double bond and two enocyclic double bonds in fulvene ligands have been bound to two Ru atoms in an η1:η5-mode. Complex 20 has been characterized by single crystal X-ray diffraction analysis and its crystal structure shows that the 6, 6-tetramethylenefulvene undergos double bond isomerization, which does not coorditate with the metal center in the reaction. These results suggest that when metal carbonyl complexes reacted with fulvenes, due to the different coordination modes, diversified product structures were obtained. Different coordination modes in molecular structures had a great influence on the Ru-Ru bond distance. The Ru-Ru bond distances of complexes in η3:η5 and η1:η5 fashions were longer than that of unbridged complexes in η5 fashion. This is mainly attributable to the existence of the C-bridge, which hindered further nearing between the two Ru atoms and made the Ru-Ru bond longer.Keywords: five-heterocyclic, fulvene, cyclopentadienyl, metal carbonyl complex, isomerizationVI学位论文原创性声明本人所提交的学位论文《金属羰基化合物与富烯以及五元杂环取代的环戊二烯的反应研究》，是在导师的指导下，独立进行研究工作所取得的原创性成果。