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

这项由无机化学、生物无机化学和金属有机化学计划颁发的奖项支持北卡罗来纳州立大学的T.Brent Gunnoe博士的研究，他利用低价Ru和铜酰胺络合物在涉及C-H和C-N键的转化中断裂和形成键。例如，联芳基普遍存在于一系列重要化合物中，包括天然产物(如萜类、木脂素、黄酮类、香豆素、单宁和各种生物碱)以及用于非线性光学的化合物、螺旋聚合物、液晶、不对称催化和氧化还原反应的配体。制备联芳键的主要方法涉及芳基卤素和有机金属芳基物种之间的交叉偶联；然而，这种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，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生产。拟议的化学旨在研究Ru和铜介导的C-C偶联反应的细节，这些反应通过C-H键的断裂进行。明确定义的Ru和铜酰胺络合物的氧化促进了这种反应，详细的机理研究和可能的催化序列扩展都将继续进行。此外，由于能够控制宏观性质，含有杂原子官能团的聚合物的合成是当前的研究热点。Ru-N-N络合物已被用来裂解C-N多键，拟议的化学将详细探索这些反应，包括可能扩展到聚合方法。教学计划描述了本科生和研究生教学中的一系列活动，包括修改系课程和高级课程，努力增加本科生的研究机会，并将一项计划整合到研究生课程中：(1)将以研究生为基础的外展计划纳入学校(6-8年级)，这些学校的人口主要由在科学中代表不足的群体组成；(2)让研究生接触当前的研究伦理主题；(3)为研究生提供指导教学经验。建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，形成许多有用产品的基础。教学计划涉及本科生和研究生的教学，包括修订系课程和高级课程，增加本科生的研究机会，并向当地学校推广。

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.