Energy Transfer to Ni-Amine Complexes in Dual Catalytic, Light-Driven C-N Cross-Coupling Reactions

Dual catalytic light-driven cross-coupling methodologies utilizing a Ni(II) salt with a photocatalyst (PC) have emerged as promising methodologies to forge aryl C-N bonds under mild conditions. The recent discovery that the PC can be omitted and the Ni(II) complex directly photoexcited suggests that...

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Veröffentlicht in:Journal of the American Chemical Society Jg. 141; H. 49; S. 19479
Hauptverfasser: Kudisch, Max, Lim, Chern-Hooi, Thordarson, Pall, Miyake, Garret M
Format: Journal Article
Sprache:Englisch
Veröffentlicht: United States 11.12.2019
ISSN:1520-5126, 1520-5126
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Abstract Dual catalytic light-driven cross-coupling methodologies utilizing a Ni(II) salt with a photocatalyst (PC) have emerged as promising methodologies to forge aryl C-N bonds under mild conditions. The recent discovery that the PC can be omitted and the Ni(II) complex directly photoexcited suggests that the PC may perform energy transfer (EnT) to the Ni(II) complex, a mechanistic possibility that has recently been proposed in other systems across dual Ni photocatalysis. Here, we report the first studies in this field capable of distinguishing EnT from electron transfer (ET), and the results are consistent with Förster-type EnT from the excited state [Ru(bpy) ]Cl PC to Ni-amine complexes. The structure and speciation of Ni-amine complexes that are the proposed EnT acceptors were elucidated by crystallography and spectroscopic binding studies. With the acceptors known, quantitative Förster theory was utilized to predict the ratio of quenching rate constants upon changing the PC, enabling selection of an organic phenoxazine PC that proved to be more effective in catalyzing C-N cross-coupling reactions with a diverse selection of amines and aryl halides.
AbstractList Dual catalytic light-driven cross-coupling methodologies utilizing a Ni(II) salt with a photocatalyst (PC) have emerged as promising methodologies to forge aryl C-N bonds under mild conditions. The recent discovery that the PC can be omitted and the Ni(II) complex directly photoexcited suggests that the PC may perform energy transfer (EnT) to the Ni(II) complex, a mechanistic possibility that has recently been proposed in other systems across dual Ni photocatalysis. Here, we report the first studies in this field capable of distinguishing EnT from electron transfer (ET), and the results are consistent with Förster-type EnT from the excited state [Ru(bpy) ]Cl PC to Ni-amine complexes. The structure and speciation of Ni-amine complexes that are the proposed EnT acceptors were elucidated by crystallography and spectroscopic binding studies. With the acceptors known, quantitative Förster theory was utilized to predict the ratio of quenching rate constants upon changing the PC, enabling selection of an organic phenoxazine PC that proved to be more effective in catalyzing C-N cross-coupling reactions with a diverse selection of amines and aryl halides.
Dual catalytic light-driven cross-coupling methodologies utilizing a Ni(II) salt with a photocatalyst (PC) have emerged as promising methodologies to forge aryl C-N bonds under mild conditions. The recent discovery that the PC can be omitted and the Ni(II) complex directly photoexcited suggests that the PC may perform energy transfer (EnT) to the Ni(II) complex, a mechanistic possibility that has recently been proposed in other systems across dual Ni photocatalysis. Here, we report the first studies in this field capable of distinguishing EnT from electron transfer (ET), and the results are consistent with Förster-type EnT from the excited state [Ru(bpy)3]Cl2 PC to Ni-amine complexes. The structure and speciation of Ni-amine complexes that are the proposed EnT acceptors were elucidated by crystallography and spectroscopic binding studies. With the acceptors known, quantitative Förster theory was utilized to predict the ratio of quenching rate constants upon changing the PC, enabling selection of an organic phenoxazine PC that proved to be more effective in catalyzing C-N cross-coupling reactions with a diverse selection of amines and aryl halides.Dual catalytic light-driven cross-coupling methodologies utilizing a Ni(II) salt with a photocatalyst (PC) have emerged as promising methodologies to forge aryl C-N bonds under mild conditions. The recent discovery that the PC can be omitted and the Ni(II) complex directly photoexcited suggests that the PC may perform energy transfer (EnT) to the Ni(II) complex, a mechanistic possibility that has recently been proposed in other systems across dual Ni photocatalysis. Here, we report the first studies in this field capable of distinguishing EnT from electron transfer (ET), and the results are consistent with Förster-type EnT from the excited state [Ru(bpy)3]Cl2 PC to Ni-amine complexes. The structure and speciation of Ni-amine complexes that are the proposed EnT acceptors were elucidated by crystallography and spectroscopic binding studies. With the acceptors known, quantitative Förster theory was utilized to predict the ratio of quenching rate constants upon changing the PC, enabling selection of an organic phenoxazine PC that proved to be more effective in catalyzing C-N cross-coupling reactions with a diverse selection of amines and aryl halides.
Author Kudisch, Max
Thordarson, Pall
Miyake, Garret M
Lim, Chern-Hooi
Author_xml – sequence: 1
  givenname: Max
  surname: Kudisch
  fullname: Kudisch, Max
  organization: Department of Chemistry , Colorado State University , Fort Collins , Colorado 80523 , United States
– sequence: 2
  givenname: Chern-Hooi
  orcidid: 0000-0003-1823-6305
  surname: Lim
  fullname: Lim, Chern-Hooi
  organization: New Iridium LLC , Boulder , Colorado 80303 , United States
– sequence: 3
  givenname: Pall
  orcidid: 0000-0002-1200-8814
  surname: Thordarson
  fullname: Thordarson, Pall
  organization: School of Chemistry, The Australian Centre for Nanomedicine and the ARC Centre of Excellence in Convergent Bio-Nano Science & Technology , The University of New South Wales , Sydney , NSW 2052 , Australia
– sequence: 4
  givenname: Garret M
  orcidid: 0000-0003-2451-7090
  surname: Miyake
  fullname: Miyake, Garret M
  organization: Department of Chemistry , Colorado State University , Fort Collins , Colorado 80523 , United States
BackLink https://www.ncbi.nlm.nih.gov/pubmed/31714761$$D View this record in MEDLINE/PubMed
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Snippet Dual catalytic light-driven cross-coupling methodologies utilizing a Ni(II) salt with a photocatalyst (PC) have emerged as promising methodologies to forge...
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Title Energy Transfer to Ni-Amine Complexes in Dual Catalytic, Light-Driven C-N Cross-Coupling Reactions
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