Dinuclear Reductive Elimination Reactions of Dimeric Platinum Complexes

制备了一系列含桥接（二苯基膦）环戊二烯基（dppc）配体的二聚体铂配合物，并用核磁共振波谱和x射线衍射对其进行了表征。双核还原消除反应将导致碳-碳键的形成，这些过程的机制将使用同位素标记和变温核磁共振技术进行研究。dppc桥接铂体系将以两种方式发展。第一种方法是在环戊二烯环上引入一个或多个甲基。这将增强配体的配位能力，并防止环戊二烯环的可逆解离，这似乎是双核消去的一个特征。其次，制备双（膦）环戊二烯基配体并用于构建同金属和异金属三聚体和低聚体配合物。当两种不同的金属存在于一个复合体中时，化学反应可能与单独的金属中的任何一种不同。在化学学部无机、生物无机和有机金属项目中，圣路易斯密苏里大学的戈登·k·安德森博士将制备二聚体铂配合物，用作碳-碳键形成反应的催化剂。这种类型的反应涉及重整过程和以乙烯、甲醇或合成气为基础的燃料生产。此外，为了同样的目的，还可以合成含有许多不同元素的金属原子的配合物。

A series of dimeric platinum complexes containing bridging (diphenylphosphino)cyclopentadienyl (dppc) ligands will be prepared and characterized by NMR spectroscopy and X-ray diffraction. Dinuclear reductive elimination reactions will result in carbon-carbon bond formation, and the mechanism(s) of these processes will be investigated using isotopic labeling and variable temperature NMR techniques. The dppc-bridged platinum system will be developed in two ways. The first will be to introduce one or more methyl groups onto the cyclopenta- dienyl ring. This will enhance the coordinating ability of the ligand and prevent reversible dissociation of the cyclopenta- dienyl ring, which appears to be a feature of the dinuclear eliminations. Secondly, a bis(phosphino)cyclopentadienyl ligand will be prepared and used to construct homo- and hetero- metallic trimeric and oligomeric complexes. Where two different metals are present in a single complex, chemistry different from that found for either metal alone is expected. %%% In this project in the Inorganic, Bioinorganic, and Organo- metallic Program of the Chemistry Division, Dr. Gordon K. Anderson of the University of Missouri at Saint Louis will prepare dimeric platinum complexes for use as catalysts in carbon-carbon bond forming reactions. This type of reaction is involved in reforming processes and the production of fuels based on ethylene, methanol, or synthesis gas. In addition, complexes containing many metal atoms of different elements will be synthesized for the same purpose.