Formation, Activation and Functionalization of Carbon-Element Bonds by Late Transition Metal Complexes

This award in the Division of Chemistry to Alan Goldman at Rutgers University centers on the oxidative addition and reductive elimination of C-H bonds by late transition metal complexes. The factors that govern the thermodynamics, kinetics and selectivity of C-H, C-C, C-X and X-H bond addition and elimination with such complexes will be elucidated. As the insertion of unsaturated substrates into M-C, M-H, and M-X bonds is likely the most difficult step in many potential catalytic cycles related to C-H activation, these insertions will also be investigated. The approach will be based on the extensive integration of: 1) The synthesis of new late metal complexes, particularly pincer-ligated metal complexes, which offer high stability together with the ability to explore variation of ancillary coordinating groups in a well controlled fashion, while leaving open coordination sites for substrate activation and subsequent steps. 2) Mechanistic studies of addition/eliminations and insertion/de-insertions. 3) Screening new complexes for a broad array of stoichiometric and catalytic reactions. The latter will include additions of CH and X-H to unsaturates (olefins, alkynes, CO), and dehydrocoupling. When the potential for asymmetric catalysis exists, chiral pincer complexes will be investigated. The reactivity of C-H addition products will be investigated with respect to functionalization of the resulting M-C and M-H bonds (e.g. insertions) and for the effect of C-H addition on remote sites (e.g. increased susceptibility toward nucleophilic attack on homo- and heteroaromatics as a result of metallation). 4) Computational (DFT) studies will be used to provide leads for synthesis. Computational methods will be tested and calibrated by mechanistic and screening studies. New functionals and basis sets will be investigated to increase predictive value, and thus the ability to design and improve new catalysts.

The development of catalytic C-H bond transformations, as well as reactions in which C-O and C-F bonds are broken or formed, has vast potential impact in areas ranging from the synthesis of fuels to pharmaceuticals. Students and postdoctoral associates will receive broad training in synthesis, analysis, and in the principles and strategy of catalyst design and development, including the use of computational methods. Graduate students, postdoctoral associates and undergraduates will gain industrial perspectives through collaboration with Chevron. Every summer, through the Project SEED program, high school students from under-represented backgrounds are exposed to research in this area and come to view of science as a portal to opportunity rather than a body of knowledge to be received.