Event



Inorganic Chemistry Seminar: Dr. Jeremy Smith, Indiana University

"New Catalysis Enabled by a Non-Innocent Imido Ligand"
Oct 18, 2022 at - | Chemistry Complex
Carol Lynch Lecture Hall
In-Person

Inquiries Rosa M. Vargas
rvargas@sas.upenn.edu

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smith

Abstract 

-Significant work has established the utility of low-coordinate iron imido complexes in two-electron nitrene group transfer reactions. We have found that strongly donating bis(carbene)borates ligands expand the scope of iron imido chemistry, including new catalytic transformations that are redox neutral. In addition to providing a platform for accessing rare examples of isolable iron(V) and iron(VI) bis(imido) complexes, a three-coordinate iron(III) imido complex also serves as an entry point to the corresponding iron(II) imido. The high spin (S = 2) state of the iron(II) complex attenuates the iron-nitrogen multiple bond character, helping to create an unusually electrophilic imido ligand with reactivity patterns akin to those of early transition metals. In addition to known transformations such as such as [2+2] cycloadditions, the iron(II) imido is active in new reactions, including the first ene-like reactivity of an imido ligand. Many of these transformations form the basis for new catalytic reactions in which the imido ligand plays a non-innocent role, including the catalytic a-deuteration of alkynes and the pKa-dictated isomerization of alkenes.

Research 

 

Professor Smith's research involves the investigation of transition metal complexes as applied to chemical transformations. This work involves the synthesis, characterization and reactivity of metal-ligand multiple bonds, the development of new scaffolds for spin-state tuning and photomagnetism in low coordination environments and the design of complexes for energy-relevant catalysis.

https://www.chem.indiana.edu/faculty/jeremy-smith/

 

Host: Dr. Mindiola