Inorganic Chemistry
Article
1168(11), 1070(12), 913(15), 829(7), 730(9), 694 (1), 578(14),
529(4).
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Synthesis of 13: At room temperature a solution of benzaldehyde
(7.2 mg, 0.068 mmol) in CH2Cl2 (0.5 mL) was added to a solution of
borole I (30.0 mg, 0.067 mmol) in CH2Cl2 (1 mL). The color changed
from dark blue to colorless immediately following the addition. After
20 min, the solvent was removed in vacuo to produce a white solid.
The solids were washed with pentane (3 × 1 mL) and dried in vacuo
to give a white powder. Yield: 34.7 mg, 91%; mp = 148−149 °C; single
crystals for X-ray diffraction studies were grown from a diethyl ether
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1
solution of 13 by vapor diffusion into hexanes. H NMR (360 MHz,
CDCl3) δ = 7.80−7.71 (m, 2H, C6H5), 7.43 (dd, J = 7.6, 5.2 Hz, 3H,
C6H5), 7.38−7.29 (m, 2H, C6H5), 7.26−7.00 (m, 11H, C6H5), 6.98−
6.89 (m, 2H, C6H5), 6.86−6.71 (m, 10H, C6H5), 5.16 (s, 1H, CH);
13C{1H} NMR (126 MHz, CDCl3) δ 151.3, 143.7, 140.8, 140.7, 140.1,
138.9, 137.2, 135.2, 135.1, 132.2, 132.1, 131.4, 130.8, 129.7, 128.6,
128.4, 127.8, 127.4, 127.1, 127.0, 126.9, 126.6, 126.3, 125.8, 125.7,
125.1, 77.4; 11B{1H} NMR (193 MHz, CDCl3) δ = 35 (br); FT-IR
(cm−1(ranked intensity)): 3054(15), 2962(9), 1597(8), 1488(6),
1437(7), 1327(13), 1259(3), 1071(12), 1010(2), 796(4), 737(11),
696(1), 587(14), 568(10), 542(5).
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Synthesis of 14: At room temperature, a solution of benzophenone
(12.3 mg, 0.067 mmol) in CH2Cl2 (0.5 mL) was added to a solution of
borole I (30 mg, 0.067 mmol) in 1 mL of CH2Cl2. The color changed
from dark blue to colorless immediately following the addition. After
30 min, the solvent was removed in vacuo to produce a white solid.
The solids were washed with hexane (3 × 1 mL) and dried in vacuo to
give 14 as a white powder. Yield: 37.2 mg, 86%; mp = 205−207 °C;
single crystals for X-ray diffraction studies were grown from a diethyl
1
ether solution of 14 by vapor diffusion into hexanes. H NMR (500
MHz, CDCl3) δ 8.23−8.21 (m, 1H), 8.03−7.89 (m, 2H), 7.79−7.70
(m, 1H), 7.55 (td, J = 7.4, 1.7 Hz, 1H), 7.51−7.36 (m, 5H), 7.10−6.85
(m, 12H), 6.85−6.75 (m, 3H), 6.75−6.61 (m, 3H), 6.61−6.53 (m,
2H), 6.27−6.16 (m, 2H);13C{1H} NMR (126 MHz, CDCl3) δ =
151.9, 148.0, 147.4, 146.9, 146.3, 146.2, 144.3, 141.7, 140.9, 140.8,
140.7, 139.6, 138.4, 135.6, 131.5, 131.0, 130.9, 130.8, 130.7, 130.2,
129.4, 128.7, 128.4, 128.3, 128.2, 127.9, 127.7, 127.6, 127.2, 127.1,
127.0, 126.8, 126.7, 126.5, 126.3, 126.2, 126.1, 126.0, 125.5, 125.4,
125.2, 87.2; 11B{1H} NMR (193 MHz, CDCl3) δ = 45 (br); FT-
IR(cm−1(ranked intensity)): 3054(9), 1597(6), 1489(3), 1441(5),
1304(15), 1265(2), 1185(12), 1072(10), 1026(7), 759(11), 737(8),
695(1), 636(14), 569(13), 543(4).
(19) Piers, W. E.; Marwitz, A. J. V.; Mercier, L. G. Inorg. Chem. 2011,
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(22) Houghton, A. Y.; Karttunen, V. A.; Fan, C.; Piers, W. E.;
Tuononen, H. M. J. Am. Chem. Soc. 2013, 135, 941.
(23) Houghton, A. Y.; Karttunen, V. A.; Piers, W. E.; Tuononen, H.
M. Chem. Commun. 2014, 50, 1295.
(24) Lewis, S. P.; Chai, J.; Collins, S.; Sciarone, T. J. J.; Henderson, L.
D.; Fan, C.; Parvez, M.; Piers, W. E. Organometallics 2009, 28, 249.
(25) Houghton, A. Y.; Hurmalainen, J.; Mansikkamaki, A.; Piers, W.
E.; Tuononen, H. M. Nat. Chem. 2014, 6, 983.
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ASSOCIATED CONTENT
* Supporting Information
■
S
X-ray data, IR and NMR spectra, structure of 15, decom-
position of 11. This material is available free of charge via the
(27) Braunschweig, H.; Fernandez, I.; Frenking, G.; Kupfer, T.
Angew. Chem., Int. Ed. 2008, 47, 1951.
AUTHOR INFORMATION
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Corresponding Author
(28) Braunschweig, H.; Kupfer, T. Chem. Commun. 2008, 4487.
(29) Braunschweig, H.; Chiu, C. W.; Radacki, K.; Brenner, P. Chem.
Commun. 2010, 46, 916.
Author Contributions
(30) Braunschweig, H.; Chiu, C. W.; Wahler, J.; Radacki, K.; Kupfer,
The manuscript was written through contributions of all
authors. All authors have given approval to the final version of
the manuscript.
T. Chem.Eur. J. 2010, 16, 12229.
(31) Braunschweig, H.; Breher, F.; Chiu, C. W.; Gamon, D.; Nied,
D.; Radacki, K. Angew. Chem., Int. Ed. 2010, 49, 8975.
(32) Braunschweig, H.; Chiu, C. W.; Radacki, K.; Kupfer, T. Angew.
Chem., Int. Ed. 2010, 49, 2041.
Notes
The authors declare no competing financial interest.
(33) Ansorg, K.; Braunschweig, H.; Chiu, C. W.; Engels, B.; Gamon,
D.; Hugel, M.; Kupfer, T.; Radacki, K. Angew. Chem., Int. Ed. 2011, 50,
2833.
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ACKNOWLEDGMENTS
This work was generously supported by the Welch Foundation
(Grant No. AA-1846) and Baylor University.
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(34) Braunschweig, H.; Kupfer, T. Chem. Commun. 2011, 47, 10903.
(35) Braunschweig, H.; Chiu, C. W.; Kupfer, T.; Radacki, K. Inorg.
Chem. 2011, 50, 4247.
(36) Braunschweig, H.; Dyakonov, V.; Jimenez-Halla, J. O. C.; Kraft,
K.; Krummenacher, I.; Radacki, K.; Sperlich, A.; Wahler, J. Angew.
Chem., Int. Ed. 2012, 51, 2977.
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