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

N医生匹兹堡大学化学系的约翰库珀是 由无机，生物无机和有机物计划支持， 化学部研究高度还原的配合物 锰。 这个项目的主要目标是利用不寻常的 反应性的四hapto锰（-I）苯络合物，以开发新的 芳烃与过渡金属配位的反应。 的 阳离子试剂的亲电性，例如六配位Mn（I） 络合物，亚胺盐，和阳离子环庚三烯基络合物，将是 用于驱动Mn（-I）络合物的添加。 这些补充是 有望产生新的联芳基配体，氨基烷基取代的配体， 和6：4：7稠环系统。 机理的基础研究， 将使用烯酮来探索这些添加的范围，并且 将测试与烯酮亚胺盐的反应以迫使进入 （2+2）加成，导致4元碳环与 苯核。 去除二烯配体的策略 也将研究从金属中心。 提出的反应 有几个共同的特点，这可能使他们的战略 在有机合成中的价值;所有这些都涉及形成新的C-C键， 苯环，许多引入有用的官能团用于合成， 所有这些都可能是立体定向的，大多数应该是可访问的， 芳烃核上的其它取代基。 苯是化学中最重要的分子之一， 拟议研究的更广泛意义在于，它将导致新的 苯的反应，不能通过传统的有机 方法.这些研究将为碳-碳键的形成提供新的线索 反应，并预计结果是一般的 用于有机合成领域。

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.