High-valent Non-oxo and Oxo Complexes of Late Transition Metals For C-H Bond Functionalization

With the support of the Chemical Synthesis (SYN) program in the Division of Chemistry, Professor Dong Wang of the University of Montana is studying novel transition metal catalysts that can be applied to convert inert hydrocarbons to their functionalized derivatives. This transformation is a key step in many processes for the production of fuels, chemicals, pharmaceuticals, clinical reagents, and agrochemicals. However, many challenges on the fundamental level remain unaddressed. In this project, Dr. Wang and his group plan to synthesize unprecedented cobalt and nickel coordination complexes using a novel tridentate ligand discovered by his group. These metal complexes are strong oxidants that can activate inert carbon-hydrogen bonds in hydrocarbon substrates and install the desired functional groups on them. Once successful, this project is expected to offer a comprehensive understanding about the relationship between the structures, spectroscopic properties and oxidative reactivities of these complexes, ultimately leading to the development of effective and selective methods to functionalize hydrocarbons. Furthermore, this project will provide a solid training ground to educate Montana middle school and high school students and teachers by expanding the outreach efforts led by Dr. Wang. This “Partnership in Chemistry (PIC)” program will provide summer research opportunities and scientific camps for Montana middle school and high school students and their science teachers. With the support of the Chemical Synthesis (SYN) program in the Division of Chemistry, Professor Dong Wang of the University of Montana is studying high-valent oxo and non-oxo complexes of first-row late transition metals cobalt and nickel for the activation and functionalization of inert aliphatic hydrocarbons. This transformation is a key step in many biological and synthetic processes, but is an unsolved challenge using earth-abundant first-row transition metal reagents. In this project, Dr. Wang and his group propose to synthesize novel high-valent cobalt and nickel complexes having unusual, formal +4 oxidation states and capable of activating strong carbon-hydrogen bonds using a rigid, tridentate, dianionic N3 ligand platform. Published and preliminary results have shown that there is an intrinsic relationship between the structures, spectroscopic properties and oxidative reactivities of these complexes. In collaboration with the Jackson group at the Kansas University, the Wang group aims to employ spectroscopic approaches to characterize these novel complexes and use computational calculations to guide rational modifications of the N3 ligand and the coordinating anions. Once successful, this research will afford ground-breaking results that advance the fundamental knowledge of the high-valent chemistry for first-row late transition metal complexes and shed light on future development of catalytic carbon-hydrogen bond functionalization methods. This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.