CAREER: Arene Functionalization by Metal Catalysts with Heavily Fluoronated Ligands

这项由无机化学、生物无机化学和金属有机化学项目颁发的职业奖支持麻省理工学院的约瑟夫·P·萨迪吉教授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。这些络合物将包含氧或氮与亲电金属中心(如铜(III))之间的非常活泼的成键排列，金属中心周围有一个有机氟口袋，该口袋不受金属中心的攻击，同时防止金属中心相互反应。拟议的铜、钯和铑配合物的反应性将受周围有机支架的性质控制。拟议的研究将给学生研究人员在有机合成、配位化学、结晶学、光谱和动力学以及催化方面的经验。课程包括合成配体和络合物，用光谱方法对它们进行表征，监测和解释关键反应的速率，以引起学生的兴趣，并为他们的独立研究做好准备。本课程将启动一个完整的、为期一学期的实验室序列，包括合成配体和络合物，并为他们的独立研究做好准备。各种防止自毁的活性金属络合物将被准备好，通过有效和环境友好的方法向有机化合物中插入新的原子或基团，以提供经济上有用的产品。参与这个项目的学生将学习合成有机分子和金属络合物，并用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.