Prof. Daniel Mindiola, University of Indiana

Organometallic Consequences of a One-Electron Oxidation

Brad C. Bailey, Falguni Basuli, Alison R. Fout, Hongjun Fan, John C. Huffman, Mu-Hyun Baik, and Daniel J. Mindiola.*
Department of Chemistry, Molecular Structure Center, and School of Informatics. Indiana University, Bloomington, IN 47405

The controlled and selective activation of inert C−H bonds of alkanes and arenes, and their functionalization to commodity products is one of the major challenges that organotransition metal chemistry faces today, and constitutes an area of intensive study. Part of the challenge lies within the inert C−H bonds that lack energetically accessible orbitals or binding sites to facilitate the activation process, unlike most substrates that are easier to activate given their inherent binding affinity. Likewise, the catalytic conversion of N-heterocycles present in petroleum or coal-based liquids to ammonia and nitrogen-free carbon based products, a process referred to as hydrodenitrogenation or HDN, is an important petrochemical transformation since it reduces the emissions of NOx upon combustion of these fuels. Unfortunately, both of these processes are high energy, inefficient, but understanding the intrinsic details for intermolecular C-H and C-N bond activation and cleavage represents a challenge given the inherent stability of these linkages. In this seminar, we present reactivity studies affiliated with a transient titanium alkylidyne functionality as well as mechanistic studies surrounding the type of transformations described above. Our systems are unique examples of well-defined homogeneous models that can promote C-H activation reactions, N-heterocycle activation and subsequent denitrogenation steps. Most notably, we can perform detailed mechanistic studies of these reactions since all of them are clean and occur under mild conditions. Understanding the intrinsic details behind the C-H and C-N bond breaking events will aid future research into the design of more efficient catalysts for important industrial reactions such as HDN, alkane metathesis, and hydrocracking.

For more information contact Dr. Jake Soper (404-894-4022).