Organometallics
Article
total compound 12 (212 mg, 0.21 mmol, 72%) was isolated as an
orange solid. Single crystals suitable for the X-ray crystal structure
analysis were obtained by slow diffusion of n-pentane into a solution of
Science 1995, 269, 814−816. (c) Zhao, Y.; Lough, A. J.; Stephan, D. W.
Chem. - Eur. J. 2011, 17, 6731−6743.
(9) (a) Wrackmeyer, B. Polyhedron 1986, 5, 1709−1721.
(b) Wrackmeyer, B.; Milius, W.; Tok, O. L.; Bubnov, Y. N. Chem. -
Eur. J. 2002, 8, 1537−1543. (c) Wrackmeyer, B.; Milius, W.; Tok, O.
L. Chem. - Eur. J. 2003, 9, 4732−4738.
1
2 in CH Cl at −40 °C. Anal. Calcd for C H BF NOPSi: C, 58.35;
2
2
49 35
15
H, 3.50; N, 1.39. Found: C, 58.57; H, 3.62; N, 1.41. Mp (decomp) =
1
51 °C.
Preparation of Compound 13. Compound 12 (101 mg, 0.1
(10) (a) Mo
Kehr, G.; Erker, G. Angew. Chem., Int. Ed. 2012, 51, 1954−1957.
(b) Mobus, J.; Galstyan, A.; Feldmann, A.; Daniliuc, C. G.; Frohlich,
̈ ̈
bus, J.; Bonnin, Q.; Ueda, K.; Frohlich, R.; Itami, K.;
mmol, 1 equiv) was dissolved in C H6 (∼3 mL), and 1,4-
6
cyclohexadiene (20 μL, 0.2 mmol, 2 equiv) was added. The resulting
solution was stirred at room temperature overnight, and then all
volatiles were removed in vacuo. n-Pentane (∼5 mL) was added and
directly removed in vacuo (to remove remaining C H ). The residue
̈
̈
R.; Strassert, C. A.; Kehr, G.; Erker, G. Chem. - Eur. J. 2014, 20,
1883−11893. (c) Mobus, J.; Malessa, K.; Frisch, H.; Daniliuc, C. G.;
Frohlich, R.; Kehr, G.; Erker, G. Heteroat. Chem. 2014, 25, 396−401.
(11) See, for comparison: Liedtke, R.; Kehr, G.; Frohlich, R.;
1
̈
6
6
̈
was purified by flash chromatography (SiO , CH Cl : n-pentane =
2
2
2
̈
1
:4). After drying in vacuo, compound 13 (94.0 mg, 0.09 mmol, 94%)
Daniliuc, C. G.; Wibbeling, B.; Petersen, J. L.; Erker, G. Helv. Chim.
Acta 2012, 95, 2515−2527.
was isolated as a colorless solid. Single crystals suitable for the X-ray
crystal structure analysis were obtained from a saturated solution of
(
12) See, for comparison: (a) Ko
̈
ster, R.; Seidel, G.; Su
ster, R.;
Seidel, G.; Klopp, I.; Kruger, C.; Kehr, G.; Suß, J.; Wrackmeyer, B.
̈
ß, J.;
compound 13 in C D6 at room temperature. Anal. Calcd for
6
Wrackmeyer, B. Chem. Ber. 1993, 126, 1107−1114. (b) Ko
̈
C H BF NOPSi: C, 58.29; H, 3.59; N, 1.29. Found: C, 58.16; H,
4
9
36
15
̈
̈
4
.08; N, 1.24. Mp (decomp) = 227 °C.
Chem. Ber. 1993, 126, 1385−1396. (c) Wrackmeyer, B.; Kehr, G.; Su
J. Chem. Ber. 1993, 126, 2221−2226. (d) Wrackmeyer, B.; Maisel, H.
E.; Suß, J.; Milius, W. Z. Naturforsch. 1996, 516, 1320−1324.
(e) Wrackmeyer, B.; Kehr, G.; Suß, J.; Molla, E. J. Organomet. Chem.
ß, J.; Molla, E. J.
̈
ß,
ASSOCIATED CONTENT
Supporting Information
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*
S
̈
1998, 562, 207−215. (f) Wrackmeyer, B.; Kehr, G.; Su
̈
Organomet. Chem. 1999, 577, 82−92. (g) Wrackmeyer, B.; Kehr, G.;
Willbold, S. J. Organomet. Chem. 1999, 590, 93−103. (h) Wrackmeyer,
̈
B.; Suß, J. Z. Naturforsch. 2002, 57b, 741−745. (i) Wrackmeyer, B.;
ization of the new compounds (PDF)
Crystal structure data for 8a, 9, 12, 13, and 14 (CIF)
Tok, O. L.; Klimkina, E. V.; Milius, W. Eur. J. Inorg. Chem. 2010, 2010,
276−2282. (j) Dierker, G.; Ugolotti, J.; Kehr, G.; Frohlich, R.; Erker,
G. Adv. Synth. Catal. 2009, 351, 1080−1088. (k) Ugolotti, J.; Kehr, G.;
Frohlich, R.; Erker, G. Chem. Commun. 2010, 46, 3016−3018.
l) Ugolotti, J.; Dierker, G.; Frohlich, R.; Kehr, G.; Erker, G. J.
2
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̈
(
̈
AUTHOR INFORMATION
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Organomet. Chem. 2011, 696, 1184−1188. (m) Ge, F.; Kehr, G.;
Daniliuc, C. G.; Erker, G. J. Am. Chem. Soc. 2014, 136, 68−71. (n) Ge,
F.; Kehr, G.; Daniliuc, C. G.; Erker, G. Organometallics 2015, 34, 229−
235. (o) Eller, C.; Kehr, G.; Daniliuc, C. D.; Stephan, D. W.; Erker, G.
Chem. Commun. 2015, 51, 7226−7229.
*
Notes
The authors declare no competing financial interest.
(
13) (a) Nichols, N. L.; Hause, C. D.; Noble, R. H. J. Chem. Phys.
955, 23, 57−61. (b) See also: Lipscomb, W. N.; Wang, F. E.; May,
W. R.; Lippert, E. L., Jr. Acta Crystallogr. 1961, 14, 1100−1101.
c) Hartung, J. Chem. Rev. 2009, 109, 4500−4517.
14) (a) Cardenas, A. J. P.; Culotta, B. J.; Warren, T. H.; Grimme, S.;
Stute, A.; Frohlich, R.; Kehr, G.; Erker, G. Angew. Chem., Int. Ed. 2011,
0, 7567−7571. (b) Sajid, M.; Kehr, G.; Wiegand, T.; Eckert, H.;
Schwickert, C.; Pottgen, R.; Cardenas, A. J. P.; Warren, T. H.;
Frohlich, R.; Daniliuc, C. G.; Erker, G. J. Am. Chem. Soc. 2013, 135,
1
ACKNOWLEDGMENTS
■
Financial support by the European Research Council is
gratefully acknowledged. T.H.W. is grateful to the American
Chemical Society Petroleum Research Fund (PRF#51971-
ND3) for financial support.
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REFERENCES
̈
■
8
882−8895. (c) Wiegand, T.; Sajid, M.; Kehr, G.; Erker, G.; Eckert, H.
(
2
1) (a) Warren, T. H.; Erker, G. Top. Curr. Chem. 2013, 334, 219−
Solid State Nucl. Magn. Reson. 2014, 61−62, 19−27. (d) de Oliveira, J.
M.; Wiegand, T.; Elmer, L.-M.; Sajid, M.; Kehr, G.; Erker, G.; Magon,
C. J.; Eckert, H. J. Chem. Phys. 2015, 142, 124201.
38. (b) Stephan, D. W.; Erker, G. Chem. Sci. 2014, 5, 2625−2641.
(
2) (a) Sajid, M.; Stute, A.; Cardenas, A. J. P.; Culotta, B. J.;
Hepperle, J. A. M.; Warren, T. H.; Schirmer, B.; Grimme, S.; Studer,
A.; Daniliuc, C. G.; Frohlich, R.; Petersen, J. L.; Kehr, G.; Erker, G. J.
(15) (a) Knauer, B. R.; Napier, J. J. J. Am. Chem. Soc. 1976, 98,
4395−4400. (b) Talsi, E. P.; Semikolenova, N. V.; Panchenko, V. N.;
Sobolev, A. P.; Babushkin, D. E.; Shubin, A. A.; Zakharov, V. A. J. Mol.
Catal. A: Chem. 1999, 139, 131−137.
̈
Am. Chem. Soc. 2012, 134, 10156−10168. (b) Pereira, J. C. M.; Sajid,
M.; Kehr, G.; Wright, A. M.; Schirmer, B.; Qu, Z.-W.; Grimme, S.;
Erker, G.; Ford, P. C. J. Am. Chem. Soc. 2014, 136, 513−519.
(
c) Liedtke, R.; Scheidt, F.; Ren, J.; Schirmer, B.; Cardenas, A. J. P.;
(16) Babiarz, J. E.; Cunkle, G. T.; DeBellis, A. D.; Eveland, D.; Pastor,
S. D.; Shum, S. P. J. Org. Chem. 2002, 67, 6831−6834.
Daniliuc, C. G.; Eckert, H.; Warren, T. H.; Grimme, S.; Kehr, G.;
Erker, G. J. Am. Chem. Soc. 2014, 136, 9014−9027.
(17) Jiang, C.; Stephan, D. W. Dalton Trans. 2013, 42, 630−637.
(18) Nicolas, J.; Guillaneuf, Y.; Lefay, C.; Bertin, D.; Gigmes, D.;
Charleux, B. Prog. Polym. Sci. 2013, 38, 63−235.
(
3) Tebben, L.; Studer, A. Angew. Chem., Int. Ed. 2011, 50, 5034−
5
068.
4) (a) Wrackmeyer, B. Coord. Chem. Rev. 1995, 145, 125−156.
b) Wrackmeyer, B. Heteroat. Chem. 2006, 17, 188−208.
6) Ekkert, O.; Kehr, G.; Frohlich, R.; Erker, G. J. Am. Chem. Soc.
011, 133, 4610−4616.
7) Ekkert, O.; Miera, G. G.; Wiegand, T.; Eckert, H.; Schirmer, B.;
Petersen, J. L.; Daniliuc, C. G.; Frohlich, R.; Grimme, S.; Kehr, G.;
Erker, G. Chem. Sci. 2013, 4, 2657−2664.
8) (a) Swenton, J. S.; Callinan, A.; Wang, S. J. Org. Chem. 1992, 57,
8−85. (b) Warner, B. P.; Millar, S. P.; Broene, R. D.; Buchwald, S. L.
(
(19) Matyjaszewski, K.; Woodworth, B. E.; Zhang, X.; Gaynor, S. G.;
Metzner, Z. Macromolecules 1998, 31, 5955−5957.
(
(
(
́ ̂
(20) (a) Sciannamea, V.; Jerome, R.; Detrembleur, C. Chem. Rev.
2008, 108, 1104−1126. (b) Hawker, C. J.; Bosman, A. W.; Harth, E.
Chem. Rev. 2001, 101, 3661−3688.
(
̈
2
(
̈
(21) (a) Liedtke, R.; Harhausen, M.; Frohlich, R.; Kehr, G.; Erker, G.
Org. Lett. 2012, 14, 1448−1451. (b) Chen, C.; Harhausen, M.;
̈
Liedtke, R.; Bussmann, K.; Fukazawa, A.; Yamaguchi, S.; Petersen, J.
̈
L.; Daniliuc, C. G.; Frohlich, R.; Kehr, G.; Erker, G. Angew. Chem., Int.
Ed. 2013, 52, 5992−5996. (c) Liedtke, R.; Tenberge, F.; Daniliuc, C.
G.; Kehr, G.; Erker, G. J. Org. Chem. 2015, 80, 2240−2248.
(
7
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