GENERATION OF TRIPLET CARBENES
X. Cattoën, D. Bourissou, Chem. Rev. 2009, 109, 3333; h) D. Martin, M.
Soleilhavoup, G. Bertrand, Chem. Sci. 2011, 2, 389.
5 6
Table 2. Crystallographic data for 18·CHB11H Cl
[
2] For leading reviews on triplet carbenes see: a) H. Tomioka, Acc.
Chem. Res. 1997, 30, 315; b) H. Tomioka, in: Reactive Intermediate
Chemistry (Eds: R. A. Moss, M. S. Platz, M. Jones, Jr), Wiley-VCH,
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Moran, B. R. Brooks, P. V. R. Schleyer, H. F. Schaefer, III, J. Am. Chem.
Soc. 2007, 129, 3763; b) A. Nemirowski, P. R. Schreiner, J. Org. Chem.
Compound
18·CHB H Cl
11 5 6
Formula
Molecular weight
Crystal system
Space group
Color
C36H38B11BrCl10.22 N2
1059.70
Orthorhobic
Pbca
Pale red
plate
[
Habit
2
007, 72, 9533.
Crystal dimens, mm
a, Å
b, Å
c, Å
α, deg
0.22 × 0.06 × 0.01
13.811(9)
32.59(2)
19.634(13)
90
[4] a) T. Itoh, Y. Nakata, K. Hirai, H. Tomioka, J. Am. Chem. Soc. 2006, 128,
957; (b) E. Iwamoto, K. Hirai, H. Tomioka, J. Am. Chem. Soc. 2003, 125,
1
4664.
[
[
[
[
5] a) K. Hirai, H. Tomioka, J. Am. Chem. Soc. 1999, 121, 10213; b) H.
Tomioka, E. Iwamoto, H. Itakura, K. Hirai, Nature 2001, 412, 626.
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129, 2383.
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Aust. J. Chem. 2010, 63, 1638.
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Matsuzaki, H. Okamoto, H. Higashikawa, K. Inoue, S. Kojima, Y.
Yamamoto, J. Am. Chem. Soc. 2013, 135, 232.
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Reed, D. Hashizume, F. Iwasaki, J. Am. Chem. Soc. 2008, 130, 6894.
11] For the attempted synthesis of stable triplet carbene protected by
alkyl groups: a) K. Hirai, K. Komatsu, H. Tomioka, Chem. Lett. 1994,
503; b) H. Tomioka, H. Okada, T. Watanabe, K. Banno, K. Komatsu,
K. Hirai, J. Am. Chem. Soc. 1997, 119, 1582; c) K. Hirai, K. Yasuda,
J. Am. Chem. Soc. 2000, 122, 398; d) T. Iikubo, K. Hirai, H. Tomioka,
Org. Lett. 2002, 4, 2261; e) Y.-M. Hu, K. Hirai, H. Tomioka, J. Phys.
Chem. A 1999, 103, 9280; f) Y.-M. Hu, K. Hirai, H. Tomioka, Chem. Lett.
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Soc. Jpn. 2001, 74, 2207; h) H. Tomioka, H. Mizuno, H. Itakura, K.
Hirai, J. Chem. Soc. Chem. Commun. 1997, 2261; i) H. Itakura, H.
Mizuno, K. Hirai, H. Tomioka, J. Org. Chem. 2000, 65, 8797.
β, deg
90
γ, deg
V, Å
Z
Dcalc, g cm
Abs coeff, mm
F(000)
90
8838(10)
8
1.593
1.582
3
ꢀ
3
ꢀ
1
4254
[
Radiation; λ, Å
Temp, K
Mo Kα, 0.71073
173(2)
[
Data collected
+h, +k, ±l
7851/0/590
0.0433
0.1152
1.026
Data/restrains/param
[I >2σ(I)]
wR (all data)
GOF
Solv. for crystallization
R
1
2
3
CH CN/ether
[
18]
2
or the SHELX-97 program. Refinement on F was carried out using full-
[
12] For the attempted synthesis of stable triplet carbene protected by
halogen atoms: a) H. Tomioka, K. Hirai, C. Fujii, Acta Chem. Scand.
1992, 46, 680; b) H. Tomioka, K. Hirai, T. Nakayama, J. Am. Chem.
Soc. 1993, 115, 1285; c) B. P. Makarov, H. Tomioka, Org. Biomol. Chem.
[18]
matrix least-squares with the SHELX-97 program.
All non-hydrogen
atoms were refined using anisotropic thermal parameters. Selected crystal-
lographic parameters are summarized in Tables 1 and 2.
2
004, 2, 1834; d) H. Tomioka, T. Watanabe, K. Hirai, K. Furukawa, T.
Takui, T. Itoh, J. Am. Chem. Soc. 1995, 117, 6376; e) H. Tomioka, M.
Hattori, K. Hirai, S. Murata, J. Am. Chem. Soc. 1996, 118, 8723.
13] H. Nishi, H. Kohno, T. Kano, Bull. Chem. Soc. Jan. 1981, 54, 1897.
Acknowledgements
[
This work was supported by Grants-in-Aid for Scientific Research
on Priority Areas (No. 24109002, Stimuli-responsive Chemical
Species) from the Ministry of Education, Culture, Sports, Science
and Technology, Japan. We thank Prof. Konrad Seppelt for oxida-
tion of 5c and helpful discussions.
[14] a) T. Suzuki, T. Kitamura, T. Sonoda, S. Kobayashi, H. Taniguchi,
J. Org. Chem. 1981, 46, 2275; b) T. Kitamura, S. Kobayashi, H.
Taniguchi, J. Org. Chem. 1982, 47, 2323; c) P. J. Kropp, S. McNeely,
R. D. Davis, J. Am. Chem. Soc. 1983, 105, 6907; d) J.-M. Verbeek, M.
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Hellings, J. Cornelisse, G. Lodder, J. Org. Chem. 2003, 68, 3205; f)
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[
15] K. Sato, M. Yano, M. Furuichi, D. Shiomi, T. Takui, K. Abe, K. Itoh, A.
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