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photophysical properties, neither the presence of electron-
rich nor electron-deficient aryl moieties at the R1 position of
pyrroloarenes 2 plays a critical role in the electrochemical
properties (Table 4, entries 1, 3, and 4).
Conclusion
[2] For a review on the reactions of transition-metal-coordinated ni-
triles, see: R. A. Michelin, M. Mozzon, R. Bertani, Coord. Chem.
A new cascade reaction of nitriles was explored and the
products generated exhibit interesting structural and physi-
cal properties. The electroluminescence properties of these
compounds are currently being investigated, as they may po-
tentially be used as organic light-emitting diodes (OLEDs).
Moreover, the synthesis of heteroatom-substituted bowl-
shaped molecules from these pyrroloarenes is underway.
À
bonds through an h2-iminoacyl complex, see: M. Tobisu, N. Chatani,
[3] a) D. Astashko, H. G. Lee, D. N. Bobrov, J. K. Cha, J. Org. Chem.
2009, 74, 5528; b) A. Joosten, J.-L. Vasse, P. Bertus, J. Szymoniak,
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b) M. M. McCormick, H. A. Duong, G. Zuo, J. Louie, J. Am. Chem.
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enynes, in the presence of gold catalysts, to give pyridines, see: f) J.
Barluenga, M. ꢅ Fernꢄndez-Rodrꢆguez, P. Garcꢆa-Garcꢆa, E. Agui-
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1
Instruments: H and 13C NMR spectra were recorded on Bruker 300 (300
and 75.5 MHz) and 500 (500 and 125 MHz) spectrometers. Mass spectra
were collected with a Bruker Daltonics Apex II30. X-ray crystal-structure
determination data were collected on a Stoe–Siemens-AED diffractome-
ter. Melting points were determined with a Bꢃchi B545 melting point ap-
paratus and are uncorrected. The electrochemical experiments were ac-
complished by using a Princeton Applied Research Corporation (PAR)
model 263 A potentiostat controlled by PAR model 270 software. A
three-electrode cell was used for the electrochemical experiments. UV
spectra were recorded by HP 8453. Photoluminescence experiments were
accomplished by Jasco FP-6300 and a Cary Eclipse fluorescence spectro-
photometer. Rhodamine 110 (Ff =0.95),[18] rhodamine 101 (Ff =0.96),[19]
and coumarin (Ff =0.73)[20] were used as the standards for the determina-
tion of quantum yields.
[8] For reviews on nickel-catalyzed reactions, see: Modern Organonick-
el Chemistry (Ed.: Y. Tamaru), Wiley-VCH, Weinheim, 2005.
[9] T.-C. Wu, C.-H. Chen, D. Hibi, A. Shimizu, Y. Tobe, Y.-T. Wu,
General procedure for the preparation of pyrroloarenes: A mixture of
the appropriate alkyne (0.50 mmol), [NiBr2ACTHNUTRGNE(NUG dppe)] (15.4 mg, 25.0 mmol),
Zn (97.5 mg, 1.50 mmol), and nitrile (3 mL) in a thick-walled Pyrex tube
was purged with nitrogen for 5 min. The sealed tube was kept in an oil
bath at 1108C for 12 h (or at 1308C for 36 h). After cooling to room tem-
perature, the suspension was filtered through a layer of Celite and the
Celite was rinsed with CH2Cl2 (30 mL). The solvent was removed from
the filtrate under reduced pressure. The residue was subjected to column
chromatography on silica gel and elution with hexane/CH2Cl2 afforded
the pyrroloarene. A suitable crystal for the X-ray diffraction analysis was
grown from CH2Cl2/MeOH (ca 20:1).
[10] For the Ni0-catalyzed cycloaddition of phenylacetylene with trime-
thylsilylnitrile to give a substituted pyrrole, in 58% yield, see: N.
[11] CCDC-784425 (2d-Me), 784426 (2j-Me), 784428 (5), and 784427 (8)
contain the supplementary crystallographic data for this paper.
These data can be obtained free of charge from The Cambridge
cif.
Kawase, A. Konishi, Y. Hirao, K. Matsumoto, H. Kurata, T. Kubo,
[13] a) T. Lendvai, T. Friedl, H. Butenschçn, T. Clark, A. de Meijere,
719; b) R. Haag, F.-M. Schꢃngel, B. Ohlhorst, T. Lendvai, H. Buten-
schçn, T. Clark, M. Noltemeyer, T. Haumann, R. Boese, A. de Mei-
lated to be 63.3 kcalmolÀ1, see: c) H. Butenschçn, A. de Meijere,
Acknowledgements
This work was supported by the National Science Council of Taiwan
(NSC 98–2113-M-006–002-MY3). We also thank Prof. S.-L. Wang and
Ms. P.-L. Chen (National Tsing Hua University, Taiwan) for the X-ray
crystal structure analyses.
[14] For an example of the insertion of benzonitrile into a Ni complex,
see: J. J. Eisch, X. Ma, K. I. Han, J. N. Gitua, C. Krꢃger, Eur. J.
[15] See the Supporting Information.
[17] a) L. Pauling, The Nature of the Chemical Bond, 3rd ed., Cornell
University Press, Ithaca, 1960; according to Zefirovꢀs definition, the
sum of the van der Waals radii of two carbon atoms is 3.42 ꢂ, see:
b) Y. V. Zefirov, Crystallogr. Rep. 1997, 42, 111.
[1] For reviews on metal-catalyzed reactions for C C bond formation,
1934
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Chem. Eur. J. 2011, 17, 1930 – 1935