CAREER: "Nucleophilic, Radical, and Electrophilic Palladium Carbene Complexes: New Types of Reactivity For Palladium"
3:20-3:40pm

Abstract

In this CAREER project funded by the Chemical Catalysis Program of the Chemistry Division, Professor Iluc is developing new tools for the selective reaction of hydrogen atoms bonded to common elements such as carbon, oxygen, boron, nitrogen and silicon. In this project, new approaches that involve metal-ligand cooperation are being developed to facilitate chemical transformations under mild conditions. This work is expected to have environmental and societal impact by providing basic knowledge that allows the development of catalytic processes involving water, alcohol, and amines, which are readily available chemical feedstocks. As the educational component of his project, Professor Iluc is developing an outreach program that focuses on mentoring of students from socio-economic groups that are underrepresented in science. The educational program provides educational opportunities for youth at the Bashor Children's Home and promotes their recruitment into science, technology, engineering, and mathematics-based careers.

The project targets (1) hydrogen transfer from the ligand to the metal and vice versa, which involves a nucleophilic carbene as part of a diphosphine pincer ligand; (2) hemilabile ligands, which incorporate olefins in a pincer architecture, in order to synthesize new untethered carbene nickel and palladium complexes; and (3) transfer of radical character from the supporting ligand to a coordinated substrate. The first class of complexes features nucleophilic carbene palladium complexes that are applied to the hydration, hydroalkoxylation, and hydroamination of olefins and other unsaturated substrates. The second class focuses on nickel and palladium and is applied to carbon (C)- silicon (Si) and C- boron (B) bond forming reactions. Finally, the third class features radical carbene palladium complexes that are applied to C-hydrogen (H) amination reactions with azides and olefin copolymerization reactions. Molecular models based on density functional theory guide these experiments. The educational project includes collaboration with the Bashor Children's Home, in Goshen, Indiana, a non-profit agency that provides help for at-risk children. In addition, the CAREER Award supports summer research activities at the University of Notre Dame. Visiting high school students work closely with graduate and undergraduate chemistry students in science activities related to research in the Iluc group.

Biography

The Iluc research group focuses on the activation of inert molecules with an emphasis on the functionalization of C–H bonds in a catalytic manner. These are imperative scientific problems since less expensive and more readily available feedstocks than those currently used could be employed to meet some of the energy demands of our society. In a broad sense, the group is interested in green chemistry both in its approach (catalysis) and emphasis on using inert substrates (activation of C-H bonds). The focus is on organometallic chemistry and especially on design of metal complexes that take advantage of latent reactivity. Two major areas are targeted: (1) the synthesis of electrophilic metal centers protected by weak interactions with a supporting ligand, and (2) the characterization of systems using metal-ligand cooperation. In the first area, goals include alkane dehydrogenation, C–C coupling of olefins with ketones and nitriles, the development of E–H (E = O, S, N, P) functionalization reactions, such as anti-Markovnikov olefin hydration, hydrothiolation, hydroamination, and hydrophosphorylation. The second project will be applied to water activation and oxygen formation without photolytic activation.

Professor Iluc studied chemistry at University Politehnica of Bucharest. In 2002, he started his Ph.D. career at the University of Chicago, where he worked under the guidance of Professor Gregory Hillhouse. His research focused on metal-ligand multiple bonds in nickel complexes supported by chelating bisphosphine ligands. During 2008-2011, he was a postdoctoral fellow at the California Institute of Technology; there he worked with Professor Robert Grubbs and focused on C-H activation reactions catalyzed by iridium complexes. He joined the Chemistry and Biochemistry Department at the University of Notre Dame in summer 2011.