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

Lei Tian; Nicholas A. Till; Bryan Kudisch; David W.C. MacMillan; Gregory D. Scholes

doi:10.1021/jacs.9b12835

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

Lei Tian, Nicholas A. Till, Bryan Kudisch, David W.C. MacMillan, Gregory D. Scholes

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84 Scopus citations

Abstract

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. 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.

Original language	English (US)
Pages (from-to)	4555-4559
Number of pages	5
Journal	Journal of the American Chemical Society
Volume	142
Issue number	10
DOIs	https://doi.org/10.1021/jacs.9b12835
State	Published - Mar 11 2020

All Science Journal Classification (ASJC) codes

Catalysis
Chemistry(all)
Biochemistry
Colloid and Surface Chemistry

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title = "Transient Absorption Spectroscopy Offers Mechanistic Insights for an Iridium/Nickel-Catalyzed C-O Coupling",

abstract = "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. 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.",

author = "Lei Tian and Till, {Nicholas A.} and Bryan Kudisch and MacMillan, {David W.C.} and Scholes, {Gregory D.}",

note = "Funding Information: L.T., N.A.T., B.K., D.W.C.M., and G.D.S acknowledge support from the Division of Chemical Sciences, Geosciences, and Biosciences, Office of Basic Energy Sciences of the U.S. Department of Energy through Grant No. DE-SC0019370. This material is based on work supported by the National Science Foundation Graduate Research Fellowship under Grant Number DGE-1656466 (to B.K.). Publisher Copyright: Copyright {\textcopyright} 2020 American Chemical Society.",

year = "2020",

month = mar,

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doi = "10.1021/jacs.9b12835",

language = "English (US)",

volume = "142",

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T1 - Transient Absorption Spectroscopy Offers Mechanistic Insights for an Iridium/Nickel-Catalyzed C-O Coupling

AU - Tian, Lei

AU - Till, Nicholas A.

AU - Kudisch, Bryan

AU - MacMillan, David W.C.

AU - Scholes, Gregory D.

N1 - Funding Information: L.T., N.A.T., B.K., D.W.C.M., and G.D.S acknowledge support from the Division of Chemical Sciences, Geosciences, and Biosciences, Office of Basic Energy Sciences of the U.S. Department of Energy through Grant No. DE-SC0019370. This material is based on work supported by the National Science Foundation Graduate Research Fellowship under Grant Number DGE-1656466 (to B.K.). Publisher Copyright: Copyright © 2020 American Chemical Society.

PY - 2020/3/11

Y1 - 2020/3/11

N2 - 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. 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.

AB - 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. 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.

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VL - 142

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EP - 4559

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 10

ER -

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

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