CAREER: Arene Functionalization by Metal Catalysts with Heavily Fluoronated Ligands

无机，生物无机和有机化学计划的这个职业奖支持马萨诸塞州理工学院的Joseph P. Sadighi教授的工作，以开发能够选择性地将原子或基团插入芳烃碳氢键的金属催化剂，例如苯中的那些。 这些络合物将在氧或氮与亲电子金属中心（例如Cu（III））之间含有非常反应性的键合布置，其中在金属中心周围具有有机氟袋，其不受金属中心的攻击，同时防止金属中心彼此反应。 铜、钯和铑配合物的反应性将由周围有机支架的性质控制。拟议的研究将使学生研究人员在有机合成、配位化学、晶体学、光谱学和动力学以及催化方面获得经验。 一个完整的，长达一个学期的实验室序列，涉及配体和络合物的合成，通过光谱方法对其进行表征，以及监测和解释关键反应的速率，将启动，以吸引学生的兴趣，并为他们的独立研究做好准备。将被制备为通过有效和环境相容的方法将新原子或基团插入有机化合物中以提供经济上有用的产品。 参与该项目的学生将学习合成有机分子和金属络合物，并通过仪器方法分析它们的反应。

This CAREER award by the Inorganic, Bioinorganic and Organometallic Chemistry program supports work by Professor Joseph P. Sadighi at the Massachusetts Institute of Technology to develop metal catalysts capable of selectively inserting atoms or groups into arene carbon-hydrogen bonds, such as those in benzene. These complexes will contain very reactive bonding arrangements between oxygen or nitrogen and an electrophilic metal center, such as Cu(III), with a organofluorine pocket around the metal center that is immune to attack by the metal center while at the same time preventing metal centers from reacting with each other. The reactivity of the proposed copper, palladium and rhodium complexes will be controlled by the nature of the surrounding organic scaffolds.The proposed research will give student researchers experience in organic synthesis, coordination chemistry, crystallography, spectroscopy and kinetics, and catalysis. An integrated, semester-long laboratory sequence involving the synthesis of ligands and complexes, characterizing them by spectroscopic methods, and monitoring and interpreting the rates of key reactions will be initiated to engage the students' interest and prepare them for their independent research.Very reactive metal complexes, which are protected against self-destruction, will be prepared to insert new atoms or groups into organic compounds to provide economically useful products by efficient and environmentally compatible methods. Students involved in this project will learn to synthesize both organic molecules and metal complexes, and to analyze their reactions by instrumental methods.