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.

无机，生物有机和有机金属化学计划的这一奖项支持北卡罗来纳州立大学的T. Brent Gunnoe博士的研究，以利用低瓦伦特ruthenium和铜和铜胺伴侣的铜，以破坏涉及C-H和C-N债券的转换中的键。 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. 制备双重连接的主要方法涉及在芳基卤素和有机金属芳基物质之间进行交叉耦合。但是，这种反应通常遭受芳基卤化物和芳基有机金属试剂多步合成的要求，在某些情况下，使用有机金属芳基化合物会导致有毒副产品的化学计量产生。 拟议的化学旨在研究通过裂解C-H键进行的钌和铜介导的C-C偶联反应的细节。 定义明确定义的弦丁和铜氨基配合物的氧化促进了这种反应，并将追求详细的机械研究和可能扩展到催化序列的反应。 此外，由于控制宏观特性的能力，含有杂原样功能的聚合物的合成具有当前感兴趣。 芳族胺氨基络合物已用于切割C-N多键，拟议的化学将详细探讨这些反应，包括可能扩展到聚合方法。 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)揭露研究生的当前研究伦理主题，（3）为研究生提供了指导的教学经验。拟议的化学旨在利用金属络合物的反应性来构建构成许多有用产品基础的小有机分子的反应性。 该教学计划涉及本科和研究生教学，包括修订部门课程和上层课程，增加了本科生的研究机会以及向当地学校推广。