Work

Photosensitized, energy transfer-mediated organometallic catalysis through electronically excited nickel(II)

Year: 2017

Type: article

Abstract: Transition metal catalysis has traditionally relied on organometallic complexes that can cycle through a series of ground-state oxidation levels to achieve a series of discrete yet fundamental fragment-coupling steps. The viability of excited-state organometallic catalysis via direct photoexcitation has been demonstrated. Although the utility of triplet sensitization by energy transfer has long been known as a powerful activation mode in organic photochemistry, it is surprising to recognize that photosensitization mechanisms to access excited-state organometallic catalysts have lagged far behind. Here, we demonstrate excited-state organometallic catalysis via such an activation pathway: Energy transfer from an iridium sensitizer produces an excited-state nickel complex that couples aryl halides with carboxylic acids. Detailed mechanistic studies confirm the role of photosensitization via energy transfer.

Source: Science

DOI: 10.1126/science.aal2490

Authors: Eric R. Welin, Chip Le, Daniela M. Arias-Rotondo, James K. McCusker, David W. C. MacMillan

Institutions: Princeton University, Michigan State University

Language: English

Topic: Radical Photochemical Reactions

Subfield: Organic Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: green

Funders: National Science Foundation, National Institutes of Health, National Institute of General Medical Sciences

Awards: Photoredox Catalysis Applications in Organometallics and Chemical Biology, G1588828791, G9000133616, Physical and Photophysical Properties of Spin-Polarized Molecules