Synthetic Entries to Early-Transition Metal Complexes Containing Terminal and Reactive Metal-Ligand Multiple Bonds

Indiana University, Bloomington IN

Investigators

Abstract

This Research award in the Inorganic and Organometallic Chemistry program supports work by Professor Daniel J. Mindiola at Indiana University to understand the behavior of highly polarized and thus reactive metal-ligand multiple bonds. Kinetics and reactivity studies of transient and terminal group 4 and 5 transition metal complexes having N (nitride), P (phosphide), CR2 (alkylidene) and CR (alkylidyne) moieties with unsaturated and saturated molecules are expected to reveal the role of the metal-ligand multiple bond during the activation of chemical inert molecules such as alkanes, arenes, N-heterocycles among many other small molecules that are exceedingly resistant towards activation and functionalization. The combination of new synthetic strategies to synthesize other unknown metal-ligand multiply bonded scaffolds composed of early 3d metals by a multielectron redox approach, by combining known organometallic transformations, or by modification of the ligand framework, will also unmask unprecedented chemistry and new transformations. By preparing high-valent compounds with metal-ligand multiple bonds the research being conducted is expected to develop new systems that can mask low-valent metal centers as well as catalyze reactions such as methane activation and functionalization, benzene ring-opening and polymerization, dehydrofluorination of hydrofluorocarbons, and the functionalization of N-heterocycles. In addition to chemical research a student based chapter developed at Indiana University, Bloomington, has been founded with the purpose of recruiting underrepresented groups into the physical sciences. Students trained in these laboratories are expected to represent a new generation of chemists who can prepare molecules designed to carry a specific function while conserving energy. However, the molecules are reactive, produce less waste and improve upon current practices used in the industrial setting. Synthesis and reactivity, in an atom-economical way, represents one of the program standard goals, especially now during this uncertain era for devising alternative sources of energy. Hence, after students understand how their system operates, they are able to make their reagent more efficient in achieving the specific goal for which it was designed.