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

高度还原配合物：芳烃与锰配位的 C-C 键形成反应 (-I)

• 批准号: 9632202
• 负责人: N. John Cooper
• 金额: $ 37万
• 依托单位: University of Pittsburgh
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 1996
• 资助国家: 美国
• 起止时间: 1996-07-01 至 2000-06-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=9632202&HistoricalAwards=false
• 关键词: Highly; Reduced; Complexes; Bond; Forming

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.

匹兹堡大学化学系的 N. John Cooper 博士得到了化学部无机、生物无机和有机金属项目的支持，致力于研究高度还原的锰络合物。 该项目的主要目标是利用四联锰(-I)苯络合物的异常反应性来开发芳烃与过渡金属配位的新反应。 阳离子试剂（例如六联锰（I）络合物、亚胺盐和阳离子环庚三烯基络合物）的亲电性将用于驱动锰（-I）络合物的加成。 这些添加预计会产生新的联芳基配体、氨基烷基取代的配体和 6:4:7 稠合环系统。 将使用烯酮探索这些加成的机理和范围的基础研究，并将测试与烯酮亚胺盐的反应，以强制进入（2+2）加成，从而导致 4 元碳环融合到苯核上。 还将研究从金属中心去除二烯配体的策略。 所提出的反应具有几个共同特征，这些特征可能使它们在有机合成中具有战略价值；所有这些都涉及与苯核形成新的C-C键，许多引入了用于合成的有用官能团，所有这些都可能是立体定向的，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，该研究的更广泛意义在于它将导致苯的新反应，这是通过传统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，其结果有望在有机合成领域具有普遍实用性。