Event Title

Redox-Inactive Lewis-Acids in the Secondary Coordination Sphere for Nitrite Reduction

Research Mentor(s)

John Gilbertson

Description

Electron-transfer reactions by redox-active transition metals often function in conjunction with redox-innocent metals. Examples found in nature include the Ca2+ cation in the oxygen evolving complex of photosystem II and the Haber-Bosch process which uses a potassium-promoted iron surface to facilitate reactivity. In this work we set out to investigate the use of Lewis acids to tune the reactivity of redox non-innocent pyridinediimine (PDI) scaffold by synthesizing a series of iron (II) PDI complexes with a 15-crown-5 ether in the secondary coordination sphere. Here we report the enhancement of reaction kinetics attributed to the redox-innocent Lewis acid in the secondary coordination sphere effectively luring in the reactive anion species to the active metal center. The increase in reaction rates were studied with a series of kinetics studies and binding experiments.

Document Type

Event

Start Date

May 2018

End Date

May 2018

Location

Chemistry

Rights

Copying of this document in whole or in part is allowable only for scholarly purposes. It is understood, however, that any copying or publication of this document for commercial purposes, or for financial gain, shall not be allowed without the author’s written permission.

Language

English

Format

application/pdf

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May 17th, 12:00 PM May 17th, 3:00 PM

Redox-Inactive Lewis-Acids in the Secondary Coordination Sphere for Nitrite Reduction

Chemistry

Electron-transfer reactions by redox-active transition metals often function in conjunction with redox-innocent metals. Examples found in nature include the Ca2+ cation in the oxygen evolving complex of photosystem II and the Haber-Bosch process which uses a potassium-promoted iron surface to facilitate reactivity. In this work we set out to investigate the use of Lewis acids to tune the reactivity of redox non-innocent pyridinediimine (PDI) scaffold by synthesizing a series of iron (II) PDI complexes with a 15-crown-5 ether in the secondary coordination sphere. Here we report the enhancement of reaction kinetics attributed to the redox-innocent Lewis acid in the secondary coordination sphere effectively luring in the reactive anion species to the active metal center. The increase in reaction rates were studied with a series of kinetics studies and binding experiments.