ACS Catalysis
Research Article
(17) Nicewicz, D. A.; Nguyen, T. M. ACS Catal. 2014, 4, 355−360.
(18) Zhang, M.; Rouch, W. D.; McCulla, R. D. Eur. J. Org. Chem.
2012, 6187−6196.
CONCLUSION
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We have demonstrated, for the first time, the use of α-
sexithiophene (α-6T) as a visible-light photoredox catalyst in
the reductive dehalogention of vic-dibromides. The resulting
photocatalytic system based on a combination of α-6T,
tetramethylenediamine (TMEDA), and visible light has been
demonstrated to reductively dehalogenate a variety of different
vic-dibromides in good to excellent yield under relatively short
irradiation times. Through examination of the thermodynamic
feasibility and rate constants of the key mechanistic steps, we
have been able to better understand the underlying
mechanisms, which contribute to the high efficiency of our
catalytic system.
(19) Rouch, W. D.; Zhang, M.; McCulla, R. D. Tetrahedron Lett.
2012, 53, 4942−4945.
(20) Sakai, J.; Taima, T.; Yamanari, T.; Saito, K. Sol. Energy Mater.
Sol. Cells 2009, 93, 1149−1153.
(21) Evans, C.; Weir, D.; Scaiano, J. C.; MacEachem, A.; Arnason, J.
T.; Morand, P.; Hollebone, B.; Leitch, L. C.; Philogegne, B. J. R.
Photochem. Photobiol. 1986, 44, 441−451.
(22) Janssen, R. A.; Moses, D.; Sariciftci, N. S. J. Chem. Phys. 1994,
101, 9519.
(23) International Union of Pure and Applied Chemistry (IUPAC) Gold
Book, 2nd Edition; McNaught, A. D., Wilkinson, A., Eds.; Blackwell
Science: Oxford, U.K., 1997.
(24) Oeter, D.; Egelhaaf, H.-J.; Ziegler, C.; Oelkrug, D.; Gopel, W. J.
Chem. Phys. 1994, 101, 6344−6352.
ASSOCIATED CONTENT
* Supporting Information
Details on reaction conditions, spectral data on products,
conversion-versus-time plots, laser flash photolysis data,
quenching plots, and NMR spectra. This material is available
■
S
(25) Lakowicz, J. R. Principles of Fluorescence Spectroscopy; Kluwer
Academic−Plenum Publishers: New York, 1999; pp 278−330.
(26) Turro, N. J.; Ramamurthy, V.; Scaiano, J. C. Modern Molecular
Photochemistry of Organic Molecules; University Science Publishers:
New York, 2010; pp 1−483.
(27) James, H. J.; Broman, R. F. Anal. Chim. Acta 1969, 48, 411−417.
(28) Yagci, Y.; Jockusch, S.; Turro, N. J. Macromolecules 2007, 40,
4481−4485.
AUTHOR INFORMATION
Corresponding Author
Notes
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(29) Aydogan, B.; Yagci, Y.; Toppare, L.; Jockusch, S.; Turro, N. J.
Macromolecules 2012, 45, 7829−7834.
(30) Fujitsuka, M.; Sato, T.; Segawa, H.; Shimidzu, T. Synth. Met.
1995, 69, 309−310.
The authors declare no competing financial interest.
(31) Ismaili, H.; Pitre, S. P.; Scaiano, J. C. Catal. Sci. Technol. 2013, 3,
935−937.
ACKNOWLEDGMENTS
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(32) Jonsson, M.; Wayner, D. D. M.; Lusztyk, J. J. Phys. Chem. 1996,
100, 17539−17543.
This work was supported by the Natural Sciences and
Engineering Research Council of Canada, the Canadian
Foundation for Innovation, and the Canada Research Chairs
Program.
(33) Michaelis, L.; E.S, H. J. Gen. Physiol. 1933, 16, 859−873.
(34) Cherevatskaya, M.; Neumann, M.; Fuldner, S.; Harlander, C.;
̈
Kummel, S.; Dankesreiter, S.; Pfitzner, A.; Zeitler, K.; Konig, B. Angew.
Chem., Int. Ed. 2012, 51, 4062−4066.
̈
̈
(35) Scaiano, J. C. In Reactive Intermediate Chemistry; Moss, R. A.,
Platz, M. S., Jones, M., Eds.; John Wiley & Sons: Hoboken, NJ, 2004;
pp 847−871.
REFERENCES
■
(1) Wuts, P. G. M.; Greene, T. W. Greene’s Protective Groups on
Organic Synthesis, 4th Edition; John Wiley & Sons: Hoboken, NJ,
2007; pp 1−16.
(36) Kim-Thuan, N.; Scaiano, J. C. Int. J. Chem. Kinet. 1984, 16,
371−377.
(2) Totten, L. A.; Jans, U.; Roberts, A. L. Environ. Sci. Technol. 2001,
35, 2268−2274.
́
(37) Lalevee, J.; Graff, B.; Allonas, X.; Fouassier, J. P. J. Phys. Chem. A
2007, 111, 6991−6998.
(3) Kuivila, H. G.; Menapace, L. W. J. Org. Chem. 1963, 28, 2165−
2167.
(4) Schubert, W. M.; Rabinovitch, B. S.; Larson, N. R.; Sims, V. A. J.
Am. Chem. Soc. 1952, 74, 4590−4592.
(5) Vijayashree, N.; Samuelson, A. G. Tetrahedron Lett. 1992, 33,
559−560.
(6) Casanova, J.; Rogers, H. R. J. Org. Chem. 1974, 39, 2408−2410.
(7) Willner, I.; Tsfania, T.; Eichen, Y. J. Org. Chem. 1990, 55, 2656−
2662.
(8) Maji, T.; Karmakar, A.; Reiser, O. J. Org. Chem. 2010, 76, 736−
739.
(9) Andrieux, C. P.; Le Gorande, A.; Savea
Chem. 1994, 371, 191−196.
(10) Vaze, A.; Rusling, J. F. Langmuir 2006, 22, 10788−10795.
(11) Bosser, G.; Paris, J. J. Chem. Soc., Perkin Trans. 2 1992, 2057−
2063.
́
nt, J.-M. J. Electroanal.
(12) Lexa, D.; Saveant, J. M.; Schaefer, H. J.; Su Khac, B.; Vering, B.;
Wang, D. L. J. Am. Chem. Soc. 1990, 112, 6162−6177.
(13) Scaiano, J. C.; Barra, M.; Krzywinski, M.; Sinta, R.; Calabrese, G.
J. Am. Chem. Soc. 1993, 115, 8340−8344.
(14) Scaiano, J. C.; Barra, M.; Sinta, R. Chem. Mater. 1996, 8, 161−
166.
(15) Pitre, S. P.; McTiernan, C. D.; Ismaili, H.; Scaiano, J. C. J. Am.
Chem. Soc. 2013, 135, 13286−13289.
(16) Ravelli, D.; Fagnoni, M.; Albini, A. Chem. Soc. Rev. 2013, 42,
97−113.
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