Direct Evidence of Visible Light-Induced Homolysis in Chlorobis(2,9-dimethyl-1,10-phenanthroline)copper(II)

The Journal of Physical Chemistry Letters
Remi FayadFelix N Castellano

Abstract

Developments in the field of photoredox catalysis that leveraged the long-lived excited states of Ir(III) and Ru(II) photosensitizers to enable radical coupling processes paved the way for explorations of synthetic transformations that would otherwise remain unrealized. While first row transition metal photocatalysts have not been as extensively investigated, valuable synthetic transformations covering broad scopes of olefin functionalization have been recently reported featuring photoactivated chlorobis(phenanthroline) Cu(II) complexes. In this study, the photochemical processes underpinning the catalytic activity of [Cu(dmp)2Cl]Cl (dmp = 2,9-dimethyl-1,10-phenanthroline) were studied. The combined results from static spectroscopic measurements and conventional photochemistry, ultrafast transient absorption, and electron paramagnetic resonance spin trapping experiments strongly support blue light (λex = 427 or 470 nm)-induced Cu-Cl homolytic bond cleavage in [Cu(dmp)2Cl]+ occurring in <100 fs. On the basis of electronic structure calculations, this bond-breaking photochemistry corresponds to the Cl → Cu(II) ligand-to-metal charge transfer transition, unmasking a Cu(I) species [Cu(dmp)2]+ and a Cl atom, thereby serving as a dep...Continue Reading

References

Jan 30, 2007·Journal of the American Chemical Society·George B ShawLin X Chen
Nov 13, 2010·Journal of the American Chemical Society·K Cory MacLeodKevin M Smith
Mar 10, 2015·The Journal of Physical Chemistry. a·Sofia GarakyaraghiFelix N Castellano
May 8, 2015·Journal of the American Chemical Society·Seung Jun HwangDaniel G Nocera
Aug 2, 2016·The Journal of Organic Chemistry·Megan H ShawDavid W C MacMillan
Feb 20, 2018·Angewandte Chemie·Leyre MarzoBurkhard König
May 3, 2019·Science·Asik HossainOliver Reiser

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Citations

Jan 30, 2021·Accounts of Chemical Research·Stavros K Kariofillis, Abigail G Doyle
Apr 8, 2021·The Journal of Organic Chemistry·Rebeca Martínez-HayaJuan E Argüello
Apr 17, 2021·Journal of the American Chemical Society·David GygiDaniel G Nocera
Aug 17, 2021·Angewandte Chemie·Mohammadjavad KarimiFrançois P Gabbaï
Oct 9, 2021·Chemical Reviews·Kelvin Pak Shing CheungVladimir Gevorgyan
Jan 13, 2022·Journal of the American Chemical Society·Miguel I GonzalezDaniel G Nocera

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