Highly Reduced Complexes: C-C Bond Forming Reactions of Arenes Coordinated to Manganese (-I)

约翰·库珀博士，匹兹堡大学化学系，由化学部无机、生物无机和有机金属计划支持，用于研究高度还原的锰配合物。这个项目的主要目标是利用四氢钼锰(-i)苯络合物的不同寻常的反应性来开发与过渡金属配位的芳烃的新反应。阳离子试剂的亲电性，如六价锰(I)络合物、亚胺盐和阳离子环庚三烯络合物，将被用来驱动向锰(-I)络合物的加成。这些加成有望产生新的联芳基配体、氨基烷基取代配体和6：4：7稠环体系。这些加成反应的机理和范围的基础研究将使用酮亚胺，并将测试与酮亚胺盐的反应，以强制进入(2，2)加成，导致四元碳环熔合到苯核上。还将研究从金属中心移除二烯配体的策略。所提出的反应有几个共同的特点，可能使它们在有机合成中具有战略价值；所有这些反应都涉及到与苯核形成新的C-C键，许多反应引入了用于合成的有用的官能团，所有这些反应都可能是立体专一性的，并且大多数应该可以与芳烃核上的其他取代基接触。苯是化学中最核心的分子之一，这项研究的更广泛的意义在于它将导致苯的新反应，这是传统的有机方法无法实现的。这些研究将为苯的碳-碳键形成反应提供新的线索，其结果有望对有机合成领域具有普遍的实用价值。

Dr. N. John Cooper, Department of Chemistry, University of Pittsburgh, is supported by the Inorganic, Bioinorganic, and Organometallic Program of the Chemistry Division for studies of highly reduced complexes of manganese. The primary objective of this project is to use the unusual reactivity of a tetrahapto Mn(-I) benzene complex to develop new reactions of arenes coordinated to transition metals. The electrophilicity of cationic reagents, such as the hexahapto Mn(I) complex, iminium salts, and cationic cycloheptatrienyl complexes, will be used to drive additions to the Mn(-I) complex. These additions are expected to produce new biaryl ligands, amino alkyl substituted ligands, and 6:4:7 fused ring systems. Fundamental studies of the mechanism and the scope of these additions will be explored using ketenes, and reactions with keteniminium salts will be tested to force entry into (2+2) additions which lead to fusion of a 4-membered carbon ring on to the benzene nucleus. Strategies for the removal of the diene ligands from the metal center will also be investigated. The reactions proposed share several characeristics which are likely to make them of strategic value in organic synthesis; all involve formation of new C-C bonds to the benzene nucleus, many introduce useful functional groups for synthesis, all are likely to be stereospecific, and most should be accessible with other substituents on the arene nucleus. Benzene is one of the most central molecules in chemistry, and the broader significance of the proposed ressarch is that it will lead to new reactions of benzene which cannot be achieved through traditional organic methods. These studies will shed new light on carbon-carbon bond forming reactions to benzene, and the results are expected to be of general utility to the field of organic synthesis.