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Chemists Break Decades-Old Chemistry Barrier with New Catalyst

Researchers have developed a catalyst that releases electrons directly into solution, breaking a long-standing rule in chemistry and potentially unlocking new reactions and molecules.

Researchers have developed a catalyst that releases electrons directly into solution, breaking a long-standing rule in...

Chemists have long relied on sophisticated molecules to develop life-saving drugs, produce advanced high-tech materials, and recreate processes found in living systems. One of the most useful tools for building these complicated structures is single-electron transfer, a technique that can activate molecules that would otherwise resist reacting and allow them to join together.

However, for decades, chemists have faced a basic limitation in how electron transfer works. When two molecules are competing to receive an electron, the electron typically goes to the molecule that is easier to reduce. This natural preference can prevent researchers from directing reactions toward other potentially useful pathways.

## A New Approach to Reaction Design

Researchers led by chemists at the University of Wisconsin-Madison have now demonstrated a different approach to reaction design. Their new strategy addresses a long-standing problem involving electron-transfer selectivity and could make a wide range of previously inaccessible coupling reactions possible.

The researchers developed a catalyst that releases the electron directly into the surrounding solution. This approach gives chemists more control over the reaction pathway and allows them to direct the electron to the desired molecule.

## Understanding the Underlying Chemistry

While the Wisconsin team developed and tested the new reaction system in the laboratory, collaborators in Colorado investigated the underlying chemistry to determine why the approach behaves so differently. Researchers at Colorado State University carried out computational studies, while scientists at the University of Colorado Boulder used spectroscopy to examine the processes controlling the new reaction framework.

The Colorado State work was led by Robert Paton with support from the National Science Foundation-funded Center for Sustainable Photoredox Catalysis (SuPRCat). The findings show that the crucial selection does not necessarily happen when the electron first moves. Instead, the outcome can be determined by what happens afterward.

## A New Framework for Designing Redox Reactions

The new approach to reaction design could expand the range of molecules that can be connected through electron-transfer chemistry. According to Zachary Wickens, a professor in the UW-Madison Department of Chemistry who led the work, "This is not just another synthetic method; it's a new way to design redox reactions."

The research team included Prof. Zachary Wickens, Joseph M. Edgecomb, Matthew D. Resmini, and Alissia F. Meyer of UW-Madison; Niket Manoj and Prof. Robert S. Paton of CSU; and Prof. Niels H. Damrauer and Arindam Sau of CU Boulder.

| Researchers | Institution | | --- | --- | | Zachary Wickens, Joseph M. Edgecomb, Matthew D. Resmini, Alissia F. Meyer | University of Wisconsin-Madison | | Niket Manoj, Robert S. Paton | Colorado State University | | Niels H. Damrauer, Arindam Sau | University of Colorado Boulder |

The findings were recently reported in Nature.

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