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Transient Absorption Spectroscopy Offers Mechanistic Insights for an Iridium/Nickel-Catalyzed C–O Coupling

Journal Article · · Journal of the American Chemical Society
DOI:https://doi.org/10.1021/jacs.9b12835· OSTI ID:1634194
 [1];  [2];  [2];  [2];  [2]
  1. Princeton Univ., NJ (United States); Princeton University
  2. Princeton Univ., NJ (United States)
+ Show Author Affiliations
We report mechanistic insights into an iridium/nickel photocatalytic C–O cross-coupling reaction from time-resolved spectroscopic studies. Using transient absorption spectroscopy, energy transfer from an iridium photocatalyst to a catalytically relevant Ni(II)(aryl) acetate acceptor was observed. Concentration-dependent lifetime measurements suggest the mechanism of the subsequent reductive elimination is a unimolecular process occurring on the long-lived excited state of the Ni(II) complex. Furthermore, we envision that our study of the productive energy-transfer-mediated pathway would encourage the development of new excited-state reactivities in the field of metallaphotocatalysis that are enabled by light harvesting.
Research Organization:
Princeton Univ., NJ (United States)
Sponsoring Organization:
National Science Foundation; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division
Grant/Contract Number:
SC0019370
OSTI ID:
1634194
Journal Information:
Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 10 Vol. 142; ISSN 0002-7863
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
mixtures
nickel
quenching
reductive elimination
transition metals