Chemistry Department Seminar

""Probing the Excited-State Reactivity of Transition-Metal Compounds Using Photophysics""

Presented by Dr. Daniela M. Arias-Rotondo, Department of Chemistry

Monday, September 23, 2019, 10:00 am — Hamilton Seminar Room, Bldg. 555

Transition metal compounds are ubiquitous throughout the chemical sciences, their presence broadly impacting fields such as organic synthesis and solar energy conversion. This talk illustrates how spectroscopic techniques can be used to understand the intricacies of reactions involving transition metal compounds towards two different applications. The first part of this presentation will focus on the conservation of spin in chemical reactions. Our group has previously shown that spin must be conserved for energy transfer to occur.1 To further our understanding of the effect of spin on other types of reactions, we have combined Ru(II) polypyridyls and Fe(III) oxo/hydroxo-bridged dimers to study how the spin state of the acceptor affects the rate of electron transfer. Through a combination of time-resolved spectroscopy and electrochemical techniques we have shown that excited spin states may be involved in electron transfer, as was predicted by Bominaar and coworkers in their studies involving metalloproteins.2 The second half of this seminar describes the use of energy transfer to activate traditional organometallic catalysts to unlock novel reactivity patterns. In particular, we studied the use of an Ir(III) photosensitizer in combination with a Ni(II) catalyst in the coupling of aryl halides and carboxylic acids.3 Mechanistic studies showed that energy transfer from the photocatalyst to the nickel species promotes the latter to an excited state that can promote a novel C-O bond formation.

Hosted by: Matt Bird

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