Inorganic Chemistry
Communication
[ P h H g C B 1 1 F1 1 ] , 3 1 [ n B u 4 N ] 2 [ C l C u C B 1 1 F1 1 ] , 3 2
{[(MeCN)4Ag3][Ag(CB11I5Br6)2}n,33 and Ph3PAuCB11H11.34
Although strong bases such as alkyllithium compounds readily
deprotonate carborane anions,35,36 compounds such as Et3Al
do not do so. We hypothesize that the presence of an excess of
amine during the formation of 3 may have increased the
basicity and reactivity of the zinc-bonded ethyl group, leading
to metalation of the carborane anion.
(19) Crystal data for 1·C6H6: monoclinic, space group P21/c, a =
15.272(1) Å, b = 15.451(1) Å, c = 14.401(1) Å, β = 114.629(5)°, V =
3089.0(4) Å3, Z = 4, μ(Cu Kα) = 9.938 mm−1, Dc = 1.661 Mg/m3,
F(000) = 1520, GOF on F2 = 1.009, R1 = 0.0515, wR2 = 0.1364 (F2,
all data), data/restraints/parameters 5336/0/347.
(20) Winstein, S.; Clippinger, E.; Fainberg, A. H.; Heck, R.;
Robinson, G. C. J. Am. Chem. Soc. 1956, 78, 328−335.
(21) Walker, D. A.; Woodman, T. J.; Hughes, D. L.; Bochmann, M.
Organometallics 2001, 20, 3772−3776.
(22) Haufe, M.; Kohn, R. D.; Kociok-Kohn, G.; Filippou, A. C. Inorg.
Chem. Commun. 1998, 1, 263−266.
Using the carborane anion [CHB11Cl11]−, a novel benzene-
coordinated cationic organozinc compound could be synthe-
sized. The high Lewis acidity of the metal center led to active
hydrosilylation catalysis, and a rare transition-metal-substituted
deprotonated carborane dianion [CB11Cl11]2− was obtained
during hydroamination catalysis.
(23) Sarazin, Y.; Wright, J. A.; Harding, D. A. J.; Martin, E.;
Woodman, T. J.; Hughes, D. L.; Bochmann, M. J. Organomet. Chem.
2008, 693, 1494−1501.
(24) Guerrero, A.; Hughes, D. L.; Bochmann, M. Organometallics
2006, 25, 1525−1527.
(25) Wright, J. H. II; Mueck, G. W.; Tham, F. S.; Reed, C. A.
Organometallics 2010, 29, 4066−4070.
ASSOCIATED CONTENT
* Supporting Information
■
S
(26) Dechy-Cabaret, O.; Martin-Vaca, B.; Bourissou, D. Chem. Rev.
2004, 104, 6147−6176.
Synthetic procedures and NMR spectra for 1 and 3 and X-ray
crystallographic data for 1 and 3 in CIF format. This material is
(27) Muller, T. E.; Hultzsch, K. C.; Yus, M.; Foubelo, F.; Tada, M.
̈
Chem. Rev. 2008, 108, 3795−3892.
(28) Doye, S. Sci. Synth. 2009, 40a, 241−304.
(29) Pissarek, J.-W.; Schlesiger, D.; Roesky, P. W.; Blechert, S. Adv.
Synth. Catal. 2009, 351, 2081−2085.
AUTHOR INFORMATION
Corresponding Author
■
(30) Crystal data for 3: triclinic, space group P1, a = 13.7222(4) Å, b
̅
= 14.7137(4) Å, c = 19.2699(8) Å, α = 95.465(2)°, β = 107.795(3)°, γ
= 117.551(2)°, V = 3152.80(21) Å3, Z = 2, μ(Cu Kα) = 5.114 mm−1,
Dc = 1.368 Mg/m3, F(000) = 1324, GOF on F2 = 1.035, R1 = 0.0676,
wR2 = 0.1708 (F2, all data), data/restraints/parameters 10441/47/
723.
ACKNOWLEDGMENTS
■
Financial support from the National Science Foundation
(Grant CHE 0718446) is gratefully acknowledged. We further
thank Manish Khandelwal for preparation of the amino-
pentenes and gas chromatography/mass spectrometry analyses.
(31) Himmelspach, A.; Zaeres, M.; Finze, M. Inorg. Chem. 2011, 50,
3186−3188.
(32) Ivanov, S. V.; Rockwell, J. J.; Polyakov, O. G.; Gaudinski, C. M.;
Anderson, O. P.; Solntsev, K. A.; Strauss, S. H. J. Am. Chem. Soc. 1998,
120, 4224−4225.
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