PREPARATIVE STUDIES ON THE FUNCTIONALIZED NEW ORGANOMETALLIC COMPOUNDS FURNISHED WITH THE pi-CONJUGATE SYSTEM

这种具有π共轭体系的配体在过渡金属中心上的配位可能使有机过渡金属配合物通过分子具有长距离的电荷分离。此外，过渡金属的特性有助于采用多种氧化态。在连接过渡金属中心的共轭体系链的远端引入吸电子或供电子取代基，可以使电子通过共振效应从金属中心流出或流向金属中心，从而导致金属的价态提升或下降。在本次研究项目中，我们打算利用我们多年来在钼、钨等6族元素的新型配合物的制备和反应方面的研究经验积累的各种复杂的制备技术，设计和合成这些通常难以制备的配合物。从而制备了一些新的有机金属配合物，这些配合物在分子中含有pi-共轭体系的配体，并通过红外和核磁共振光谱以及x射线晶体学研究对所得到的配合物进行了表征。在本研究项目中制备和检测的新配合物可分为三类：1。含(1)4-取代邻苯二胺和(2)4-取代儿茶酚配体的钼、钨与二膦配体的氢化配合物。与对取代苯氧基配体配位的茂钼阳离子衍生物。二茂铁基衍生物在一个cp环上同时具有共轭给电子取代基，如甲基苯并二硫代烟酸基团或氨基，在另一个cp环上具有接受电子取代基，如对硝基苯基或甲酰基。

Coordination of such ligand that possesses pi-conjugate system onto the transition metal center may possibly provide the organo-transition metal complexes with a long distance charge separation through the molecule. In addition, this is facilitated with the characteristics of the transition metal to adopt a wide variety of the oxidation states. Introduction of the elctron-withdrawing or-donating substituent on the far end of the chain of the conjugated system connected to the transition metal center may cause the electron to flow by the resonance effect either from or to the metal center, resulting in promotion or descent of the valency state of the metal. In the present research project, we intended to design and synthesize these sorts of complexes, which are usually hard to be prepared, by utilizing vairous sophisticated preparation techniques accumulated through long years of our research experiences on the preparation and reactions of the new complexes of the group 6 elements such as molybdenum and tungsten. The preparation of some new organometallic complexes which possess the ligand incorporating the pi-conjugate system in the molecule was thus achieved and the resulting complexes were characterized by IR and NMR spectroscopies as well as through X-ray crystallographic studies. The new complexes prepared and examined in the present research project are categorized into three groups a follows :1. The hydrido complexes of molybdenum and tungsten with diphosphine ligand which contain(1) 4-substituted phthalimide moiety and (2) 4-substituted catecholato ligand.2. The cationic molybdenocene derivatives coordinated with p-substituted phenoxo ligand3. The ferrocenyl derivatives bearing both of conjugated electron donatign substituents such as methylbenzodithiolato moiety or amino group in one cp ring and elctron accepting substituents such as p-nitrophenylethenyl group or formyl group in another cp ring.