Organometallics
Article
mixture turned cloudy brown-green and was stirred at room
temperature overnight. The cloudy brown-green solution was filtered
through Celite to remove KBr. A solution of 18C6 (0.2380 g, 0.9011
mmol) in THF was added, the resultant green-brown solution was
stirred for 3 h and filtered to remove more residual KBr, and THF was
removed in vacuo. The resulting green-brown oil was triturated three
times with diethyl ether. The product was dissolved in diethyl ether,
and the green solution was decanted. Yellow powders were then
recrystallized from THF and diethyl ether. Recrystallization resulted in
large yellow plates, which were isolated in 10% yield based on Cu
(0.0512 g). Large yellow crystals suitable for single-crystal X-ray
diffraction were then grown at −35 °C. UV−vis (THF; λmax, nm (ε,
(5) Willert-Porada, M. A.; Burton, D. J.; Baenziger, N. C. Chem.
Commun. 1989, 1633.
(6) Naumann, D.; Roy, T.; Tebbe, K. F.; Crump, W. Angew. Chem.,
Int. Ed. 1993, 32, 1482.
(7) Furuta, H.; Maeda, H.; Osuka, A. J. Am. Chem. Soc. 2000, 122,
803.
(8) Santo, R.; Miyamoto, R.; Tanaka, R.; Nishioka, T.; Sato, K.;
Toyota, K.; Obata, M.; Yano, S.; Kinoshita, I.; Ichimura, A.; Takui, T.
Angew. Chem., Int. Ed. 2006, 45, 7611.
(9) Bertz, S. H.; Cope, S.; Murphy, M.; Ogle, C. A.; Taylor, B. J. J.
Am. Chem. Soc. 2007, 129, 7208.
(10) Gaertner, T.; Henze, W.; Gschwind, R. M. J. Am. Chem. Soc.
2007, 129, 11362.
(11) Bertz, S. H.; Cope, S.; Dorton, D.; Murphy, M.; Ogle, C. A.
Angew. Chem., Int. Ed. 2007, 46, 7082.
(12) Bartholomew, E. R.; Bertz, S. H.; Cope, S.; Murphy, M.; Ogle,
C. A. J. Am. Chem. Soc. 2008, 130, 11244.
(13) Bartholomew, E. R.; Bertz, S. H.; Cope, S. K.; Murphy, M. D.;
Ogle, C. A.; Thomas, A. A. Chem. Commun. 2010, 46, 1253.
(14) Bertz, S. H.; Hardin, R. A.; Murphy, M. D.; Ogle, C. A.; Richter,
J. D.; Thomas, A. A. J. Am. Chem. Soc. 2012, 134, 9557.
(15) Ribas, X.; Jackson, D. A.; Donnadieu, B.; Mahia, J.; Parella, T.;
Xifra, R.; Hedman, B.; Hodgson, K. O.; Llobet, A.; Stack, T. D. P.
Angew. Chem., Int. Ed. 2002, 41, 2991.
(16) Xifra, R.; Ribas, X.; Llobet, A.; Poater, A.; Duran, M.; Sola, M.;
Stack, T. D. P.; Benet-Buchholz, J.; Donnadieu, B.; Mahia, J.; Parella,
T. Chem. Eur. J. 2005, 11, 5146.
(17) Huffman, L. M.; Casitas, A.; Font, M.; Canta, M.; Costas, M.;
Ribas, X.; Stahl, S. S. Chem. Eur. J. 2011, 17, 10643.
(18) Casitas, A.; Ioannidis, N.; Mitrikas, G.; Costas, M.; Ribas, X.
Dalton Trans. 2011, 40, 8796.
(19) Huffman, L. M.; Stahl, S. S. J. Am. Chem. Soc. 2008, 130, 9196.
(20) Huffman, L. M.; Stahl, S. S. Dalton Trans. 2011, 40, 8959.
(21) King, A. E.; Huffman, L. M.; Casitas, A.; Costas, M.; Ribas, X.;
Stahl, S. S. J. Am. Chem. Soc. 2010, 132, 12068.
M
−1 cm−1)): 212 sh (24350), 249 (2523), 385 (251). Anal. Calcd for
{{K(18C6)}[Cu(OC(C6H4)(CF3)2)2]}, KC30H32O8F12Cu: C, 42.32;
1
H, 3.79; F, 26.78. Found: C, 42.53; H, 3.98; F, 26.53. H NMR (δ,
4
3
ppm, d8-THF): 3.53 (s, 24H); 6.87 (dd, Jc′ = 7.3 Hz, Jc′ = 14.6 Hz,
2H, Hc′); 6.96 (dd, 4Jb′ = 7.3 Hz, 3Jb′ = 14.6 Hz, 2H, Hb′); 7.04 (dd, 4Jd′
= 1.4 Hz, 3Jd′ = 7.3 Hz, 2H, Hd); 7.44 (br d, J = 8.0 Hz, 2H, Ha′). H
1
NMR resonances were assigned according to results of a 1H−1H
COSY spectrum (Figure S10, Supporting Information). 13C NMR (δ,
ppm, d8-THF): 71.09 (s, C12H24O6); 124.06 (s, Cd); 125.68 (s, Cc′);
127.70 (s, Cb′); 133.05 (s, Ca′); 154.49 (s, OC(ipso-C6H4)(CF3)2);
176.00 (s, OC(ortho-metalated-C6H4)(CF3)2). 13C NMR signals were
assigned according to the results of a 1H−13C HSQC spectrum
(Figure S11, Supporting Information). 19F NMR (δ, ppm, d8-THF):
−75.76 (s).
ASSOCIATED CONTENT
■
S
* Supporting Information
1
Figures, tables, and CIF files, X-ray crystallographic data, H
1
1
NMR, 19F NMR, UV−vis, H−1H COSY, and H−13C HSQC
spectra, and Cambridge Structural Database search parameters.
This material is available free of charge via the Internet at
911312 (4), and 911315 (5) also contain supplementary
crystallographic data for this paper. These data can also be
obtained free of charge from The Cambridge Crystallographic
(22) Casitas, A.; King, A. E.; Parella, T.; Costas, M.; Stahl, S. S.;
Ribas, X. Chem. Sci. 2010, 1, 326.
(23) Yao, B.; Wang, D.-X.; Huang, Z.-T.; Wang, M.-X. Chem.
Commun. 2009, 2899.
(24) Wang, Z.-L.; Zhao, L.; Wang, M.-X. Org. Lett. 2011, 13, 6560.
(25) Yao, B.; Wang, Z.-L.; Zhang, H.; Wang, D.-X.; Zhao, L.; Wang,
M.-X. J. Org. Chem. 2012, 77, 3336.
(26) Willis, C. J. Coord. Chem. Rev. 1988, 88, 133.
(27) Wang, Z.-L.; Zhao, L.; Wang, M.-X. Chem. Commun. 2012, 48,
9418.
AUTHOR INFORMATION
Corresponding Author
*L.H.D.: fax, +001-617-353-6466; tel, +001-617-358-4335; e-
■
Author Contributions
(28) Cantalupo, S. A.; Lum, J. S.; Buzzeo, M. C.; Moore, C.;
DiPasquale, A. G.; Rheingold, A. L.; Doerrer, L. H. Dalton Trans.
2010, 39, 374.
(29) Zheng, B. N.; Miranda, M. O.; DiPasquale, A. G.; Golen, J. A.;
Rheingold, A. L.; Doerrer, L. H. Inorg. Chem. 2009, 48, 4274.
(30) Cantalupo, S. A.; Ferreira, H. E.; Bataineh, E.; King, A. J.;
Petersen, M. V.; Wojtasiewicz, T.; DiPasquale, A. G.; Rheingold, A. L.;
Doerrer, L. H. Inorg. Chem. 2011, 50, 6584.
(31) Purdy, A. P.; George, C. F. Inorg. Chem. 1991, 30, 1969.
(32) Lum, J. S.; Tahsini, L.; Golen, J. A.; Moore, C.; Rheingold, A. L.;
Doerrer, L. H. Chem. Eur. J. 2013, 19, 6374.
(33) Buzzeo, M. C.; Iqbal, A. H.; Long, C. M.; Millar, D.; Patel, S.;
Pellow, M. A.; Saddoughi, S. A.; Smenton, A. L.; Turner, J. F. C.;
Wadhawan, J. D.; Compton, R. G.; Golen, J. A.; Rheingold, A. L.;
Doerrer, L. H. Inorg. Chem. 2004, 43, 7709.
The manuscript was written through contributions of all
authors. All authors have given approval to the final version of
the manuscript.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
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We thank Professor John K. Snyder for helpful discussions,
Boston University, NSF-CHE 0619339 (NMR spectrometer at
Boston University), and NSF-CHE 0910647 (L.H.D.) for
financial support.
REFERENCES
(34) Martin, J. C. Science 1983, 221, 509.
■
(35) Allen, F. H. Acta Crystallogr., Sect. B: Struct. Sci. 2002, B58, 380.
(36) Denmark, S. E.; Jacobs, R. T.; Dai-Ho, G.; Wilson, S.
Organometallics 1990, 9, 3015.
(1) Sperotto, E.; van Klink, G. P. M.; van Koten, G.; de Vries, J. G.
Dalton Trans. 2010, 39, 10338.
(2) Beletskaya, I. P.; Cheprakov, A. V. Coord. Chem. Rev. 2004, 248,
2337.
(37) Akiba, K.; Nakata, H.; Yamamoto, Y.; Kojima, S. Chem. Lett.
1992, 1559.
(3) Hickman, A. J.; Sanford, M. S. Nature 2012, 484, 177.
(4) Ribas, X.; Casitas, A. In Ideas in Chemistry and Molecular Sciences:
Where Chemistry Meets Life; Pignataro, B., Ed.; Wiley-VCH: Weinheim,
Germany, 2010; p 31.
(38) Jiang, X.-D.; Yamamoto, Y. J. Organomet. Chem. 2010, 695, 740.
(39) Yoshida, S.; Yasui, M.; Iwasaki, F.; Yamamoto, Y.; Chen, X.;
Akiba, K. Acta Crystallogr., Sect. B: Struct. Sci. 1994, B50, 151.
G
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