CAREER: Ru and Cu Amido Complexes: Aryl Coupling, C-H Activation and C-N Multiple Bond Metathesis Reactions

职业：Ru 和 Cu 氨基配合物：芳基偶联、C-H 活化和 C-N 多键复分解反应

• 批准号: 0238167
• 负责人: Thomas Gunnoe
• 金额: $ 48万
• 依托单位: North Carolina State University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2003
• 资助国家: 美国
• 起止时间: 2003-01-15 至 2008-04-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0238167&HistoricalAwards=false
• 关键词: CAREER; Ru; Cu; Amido; Complexes

This award by the Inorganic, Bioinorganic and Organometallic Chemistry program supports research by Dr. T. Brent Gunnoe of North Carolina State University to exploit low valent ruthenium and copper amido complexes to break and form bonds in transformations involving C-H and C-N bonds. For example, biaryl moieties are prevalent in an array of important compounds including natural products (e.g., terpenes, lignanes, flavonoids, coumarins, tannins and various alkaloids) as well as compounds for nonlinear optics, helical polymers, liquid crystals, ligands for asymmetric catalysis and for use in redox reactions. The leading methods for preparation of biaryl linkages involve cross coupling between aryl halogen and organometallic aryl species; however, such reactions often suffer from the requirement of multi-step syntheses of aryl halide and aryl organometallic reagents, and, in some cases, the use of organometallic aryl compounds results in the stoichiometric production of toxic byproducts. The proposed chemistry seeks to study the details of ruthenium and copper-mediated C-C coupling reactions that proceed via cleavage of C-H bonds. Oxidation of well-defined ruthenium and copper amido complexes promotes such reactions, and both detailed mechanistic studies and possible extension to catalytic sequences will be pursued. In addition, the synthesis of polymers that contain heteroatomic functionality is of current interest due to the ability to control macroscopic properties. Ruthenium amido complexes have been used to cleave C-N multiple bonds, and the proposed chemistry will explore these reactions in detail including possible extension to polymerization methodologies. The teaching plan describes a range of activities in both undergraduate and graduate instruction including revision of the departmental curriculum and upper level courses, working toward increased research opportunities for undergraduates, and integration of a program into the graduate curriculum that: (1) incorporates a graduate student-based outreach program to schools (grades 6th - 8th) whose populations are comprised primarily of groups that are underrepresented in the sciences (2) exposes graduate students to current topics of research ethics and (3) provides graduate students with a guided teaching experience.The proposed chemistry seeks to exploit the reactivity of metal complexes for the construction of small organic molecules that form the foundation for many useful products. The teaching plan involves both undergraduate and graduate instruction including revision of the departmental curriculum and upper level courses, increasing research opportunities for undergraduates and outreach to local schools.

这个奖项由无机，生物无机和有机化学计划支持研究博士T。布伦特Gunnoe的北卡罗来纳州州立大学，利用低价钌和铜的氨基配合物，打破和形成键的转换涉及C-H和C-N键。 例如，联芳基部分普遍存在于一系列重要化合物中，包括天然产物（例如，萜烯、木脂素、类黄酮、香豆素、单宁和各种生物碱）以及用于非线性光学、螺旋聚合物、液晶、用于不对称催化和用于氧化还原反应的配体的化合物。 制备联芳基键的主要方法涉及芳基卤素和有机金属芳基物质之间的交叉偶联;然而，此类反应通常需要芳基卤化物和芳基有机金属试剂的多步合成，并且在某些情况下，有机金属芳基化合物的使用导致有毒副产物的化学计量产生。 拟议的化学旨在研究钌和铜介导的C-C偶联反应的细节，通过裂解C-H键进行。 氧化的定义明确的钌和铜的酰胺络合物促进这样的反应，和详细的机理研究和可能的扩展到催化序列将被追求。 此外，合成含有杂原子官能团的聚合物是目前的兴趣，由于控制宏观性能的能力。 钌酰胺络合物已被用于裂解C-N多重键，所提出的化学将详细探讨这些反应，包括可能的延伸聚合方法。 该教学计划描述了一系列的活动，在本科和研究生教学，包括部门课程和上层课程的修订，努力增加本科生的研究机会，并将一个程序整合到研究生课程：（1）将以研究生为基础的外展计划纳入学校（6 - 8年级），其人口主要由科学领域代表性不足的群体组成（2）使研究生接触当前的研究伦理主题，（3）为研究生提供指导性的教学经验。拟议的化学旨在利用金属络合物的反应性来构建小有机分子，这些分子构成许多有用产品的基础。 教学计划涉及本科生和研究生教学，包括修订部门课程和高级课程，增加本科生的研究机会和与当地学校的联系。