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20081008III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(5-C5Me4C4H3S)M(CO)(-CO)2 M=Ru (6), M=Mo (7)、(5-C5H4)CR1R2(C4H3S)Ru (CO)22 R1, R2=CH3 (8), R1=CH3, R2=C2H5 (9), R1, R2=(CH2)5 (10), R1, R2=C2H5 (11), (5-C5Me4(2-CH3C4H2O)Ru(CO)(-CO)2 (13)和(5-C5Me4(2-CH3C4H2O)Fe(CO) (-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(3:5-C5H4C(CH2)2)Ru2(CO)5 (18)和(3:5-C5H4C(CHCH2)(C2H5)Ru2(CO)5 (19)，晶体结构显示：分子中的环戊二烯以 5的形式与一个 Ru 原子配位，离域的烯丙基以 3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 5模式配位的配合物(5-C5H4C5H7)2Ru2(CO)2(-CO)2 (20)和以 1:5模式配位的富烯桥连 Ru-Ru 键配合物(1:5-C5H4C5H8)Ru2(CO)6 (21)， 通过红外光谱、 核磁共振IV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 1:5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 3:5和 1:5模式配位的富烯桥连配合物比只以 5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 VAbstract Increasing 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 (5-C5Me4C4H3S)M(CO)(-CO)2 M=Ru (6), M=Mo (7), (5-C5H4)CR1R2(C4H3S)Ru (CO)22 R1, R2=CH3 (8), R1=CH3, R2=C2H5 (9), R1, R2=(CH2)5 (10), R1, R2=C2H5 (11), (5-C5Me4(2-CH3C4H2O)Ru(CO)(-CO)2 (13) and (5-C5Me4(2-CH3C4H2O)Fe(CO) (-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 complexes VI(3:5-C5H4C(CH2)2)Ru2(CO)5 (18) and (3:5-C5H4C(CHCH2)(C2H5)Ru2(CO)5 (19) were obtained which contain Ru-Ru bond. One Ru atom is coordinated with cyclopentadienyl ligand in 5 manner, the other Ru atom is coordinated with allyl group in 3 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 (5-C5H4C5H7)2Ru2(CO)2(-CO)2 (20) and (1:5-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 1:5-mode. Complex 20 has been characterized by single crystal X-ray diffraction an