Journal
SCIENCE
Volume 355, Issue 6323, Pages 380-384Publisher
AMER ASSOC ADVANCEMENT SCIENCE
DOI: 10.1126/science.aal2490
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Funding
- National Institute of General Medical Sciences (NIGMS), NIH [R01 GM078201-05]
- NSF [CHE-1300096]
- Division Of Chemistry
- Direct For Mathematical & Physical Scien [1300096] Funding Source: National Science Foundation
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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.
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