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Ly et al.
12
Cu[GaCl4]11 and cyclo-t-Bu4Sb4 were prepared according to
reported procedures. The NMR spectra were collected on a Bruker
AM-200 spectrometer. IR spectra were acquired using KBr pellets
on a Nicolet Nexus 470 spectrophotometer in the 4000-400 cm-1
region. Mass spectra and elemental analyses were performed by
the Analytical Instrumentation Laboratory, Department of Chem-
istry, University of Calgary.
tion of self-assembled mono- and bidimensional polymers
involving monovalent d10 metal cations. The reaction of
[{CpMo(CO)2}2(µ,η2-P2)] (Cp ) cyclopentadiene) with
AgNO3 or CuX (X ) Cl, Br, and I) resulted in the formation
of monodimensional polymers.8a,d Further studies were
conducted with the sandwich complex [Cp*Fe(η5-P5)], which
produced mono- and bidimensional coordination polymers
in reaction with different Cu(I) halides.8b The same synthon
was used for the self-assembly of a spectacular spherical
fullerene-like structure having a [Cp*Fe(η5-P5)]12(CuCl)15
framework.8c In contrast to the polymers described above,
the latter complex dissolved in organic solvents without
decomposition. Finally, the formation of cyclic antimony
ligands has been observed in the reaction of CuCl with LiSb-
(SiMe3)2 in the presence of a chelating phosphine. The
resulting cluster contained in situ formed Sb3 units coordi-
nated to copper.9
Synthesis of [{CpMo(CO)2}2(µ,η2-Sb2)], 1. A mixture of cyclo-
t-Bu4Sb4 (1 g, 1.39 mmol) and [CpMo(CO)3]2 (0.684 g, 1.39 mmol)
was stirred in decaline (50 mL) at 120 °C for 1 h and subsequently
at 190 °C for another 2 h. The reaction mixture was allowed to
cool to room temperature, and the solvent was removed in vacuo
leaving behind a dark residue that was washed with hexane and
extracted with toluene (2 × 50 mL). Upon evaporation of the
solvent, dark red crystals of 1 (584 mg, 0.862 mmol, 62%) were
obtained. The analytical data were in agreement with the reported
values.2b,5 1H NMR (C6D6, 25 °C, δ): 5.09 (s, C5H5). IR (cm-1):
1919, 1886 [ν(CO)].
Synthesis of [{CpMo(CO)2}2(µ,η2-Sb2)(µ-CuCl)]2, 2. A solu-
tion of CuCl (17 mg, 0.177 mmol) in CH3CN (3 mL) was layered
over a solution of 1 (60 mg, 0.088 mmol) in CH2Cl2 (10 mL). Dark
red crystals of 2 (60 mg, 0.077 mmol, 87%) were deposited after
1 week at room temperature and were isolated.
Elem anal. Calcd for C28H20Cl2Cu2Mo4O8Sb4 (%): C, 21.65; H,
1.30. Found: C, 21.73; H, 1.05. 1H NMR (CD2Cl2, 25 °C, δ): 5.134
(s, C5H5). IR (cm-1): 1933, 1896, 1868 [ν(CO)]. ESI-MS (m/z,
relative intensity): 1517(5) [M - Cl]+, 1419(20) [{[CpMo-
(CO)2]2Sb2Cu}]+, 1194(75) [{Cp2Mo2Sb2}2Cu]+, 971(15) [Cp2Mo3-
Sb4Cu]+, 629(100) [(CpMoSb)2Cu]+.
Synthesis of [{CpMo(CO)2}2(µ,η2-Sb2)(µ-CuBr)]2, 3. A solu-
tion of CuBr (25 mg, 0.177 mmol) in CH3CN (3 mL) was layered
over a solution of 1 (60 mg, 0.088 mmol) in CH2Cl2 (10 mL). The
formation of dark red crystals of 3 (50 mg, 0.061 mmol, 70%) was
induced through the storage of the solution at -30 °C for 2 days,
and the crystals were isolated by decanting off the mother liquor.
Elem anal. Calcd for C28H20Br2Cu2Mo4O8Sb4 (%): C, 20.48;
The formation of supramolecular aggregates through self-
organization has received considerable attention in recent
years.10 The self-organization process proved to be very
sensitive to numerous factors such as the nature of the
coordination site, the structure of the bridging ligand, the
geometric preferences of the metal ions, and the solvent. We
were interested in the potential of tetrahedral clusters
containing substituent-free antimony ligands as precursors
for the generation of self-assembled structures, and we report
here the synthesis and structural characterization of oligo-
meric and polymeric [{CpMo(CO)2}2(µ,η2-Sb2)]-CuX ad-
ducts (X ) Cl, Br, I, and GaCl4). To our knowledge, the
coordination chemistry of complexes containing Sbn ligands
has not yet been investigated. Complexes containing Sb3
units, however, displayed interesting associations through
Sb‚‚‚Sb interactions in the solid state.4c
1
H, 1.23. Found: C, 20.76; H, 1.34. H NMR (CD2Cl2, 25 °C, δ):
5.169 (s, C5H5). IR (cm-1): 1939, 1897, 1866 [ν(CO)]. ESI-MS
(m/z, relative intensity): 1564(30) [M - Br]+, 1419(85) [{[CpMo-
(CO)2]2Sb2Cu}]+, 1194(100) [{Cp2Mo2Sb2}2Cu]+, 971(30) [Cp2-
Mo3Sb4Cu]+, 628(50) [(CpMoSb)2Cu]+.
Experimental Section
General Data. All operations were performed under an argon
atmosphere using standard Schlenk and glovebox techniques.
Solvents were dried and deoxygenated, SbCl3 was sublimed, and
Mg metal was activated in situ using dibromoethane prior to use.
Synthesis of [{CpMo(CO)2}2(µ,η2-Sb2)(µ-CuI)]∞, 4. A solution
of CuI (34 mg, 0.177 mmol) in CH3CN (3 mL) was added to a
solution of 1 (60 mg, 0.088 mmol) in CH2Cl2 (10 mL). The slow
evaporation of the solvent produced dark red crystals of 4 (30 mg,
0.068 mmol, 77%).
Elem anal. Calcd for C28H20I2Cu2Mo4O8Sb4 (%): C, 19.15; H,
1.15; N, 0.40. Found: C, 19.44; H, 1.11; N, 0.71. 1H NMR (CD2-
Cl2, 25 °C, δ): 5.107 (s, C5H5), 1.974 (s, CH3CN). IR (cm-1): 1941,
1908, 1888, 1871 [ν(CO)]. ESI-MS (m/z, relative intensity): 1610-
(10) [M - I]+, 1419(60) [{[CpMo(CO)2]2Sb2Cu}]+, 1194(80)
[{Cp2Mo2Sb2}2Cu]+,971(30)[Cp2Mo3Sb4Cu]+,629(100)[(CpMoSb)2Cu]+.
Synthesis of [{CpMo(CO)2}2(µ,η2-Sb2)]4Cu2[GaCl4]2, 5. A
solution of Cu[GaCl4] (20 mg, 0.072 mmol) in toluene (5 mL) was
layered over a solution of 1 (50 mg, 0.073 mmol) in CH2Cl2 (10
mL). Diffusion was completed after 1 week, and the orange-brown
(7) (a) Cecconi, F.; Ghilardi, C. A.; Midollini, S.; Orlandini, A. J. Chem.
Soc., Chem. Commun. 1982, 229-230. (b) Cecconi, F.; Ghilardi, C.
A.; Midollini, S.; Orlandini, A. Angew. Chem., Int. Ed. Engl. 1983,
22, 554-555; Angew. Chem. 1983, 95, 554-555. (c) Di Vaira, M.;
Rovai, D.; Stoppioni, P. Polyhedron 1990, 9, 2477-2481. (d) Di Vaira,
M.; Stoppioni, P.; Peruzzini, M. J. Chem. Soc., Dalton Trans. 1990,
109-113. (e) Di Vaira, M.; Ehses, M. P.; Peruzzini, M.; Stoppioni,
P. Polyhedron 1999, 18, 2331-2336.
(8) (a) Bai, J.; Virovets, A. V.; Scheer, M. Angew. Chem., Int. Ed. 2002,
41, 1737-1740; Angew. Chem. 2002, 114, 1808-1811. (b) Bai, J.;
Leiner, E.; Scheer, M. Angew. Chem., Int. Ed. 2002, 41, 783-786;
Angew. Chem. 2002, 114, 820-823. (c) Bai, J.; Virovets, A. V.;
Scheer, M. Science 2003, 300, 781-783. (d) Scheer, M.; Gregoriades,
L.; Bai, J.; Sierka, M.; Brunklaus, G.; Eckert, H. Chem.sEur. J. 2005,
11, 2163-2169.
(9) Besinger, J.; Treptow, J.; Fenske, D. Z. Anorg. Allg. Chem. 2002, 628,
512-515.
(11) Schmidbaur, H.; Bublak, W.; Huber, B.; Reber, G.; Mu¨ller, G. Angew.
Chem., Int. Ed. Engl. 1986, 25, 1089-1090; Angew. Chem. 1986, 98,
1108-1109.
(12) (a) Issleib, K.; Hamann, B.; Schmidt, L. Z. Anorg. Allg. Chem. 1965,
339, 298-303. (b) Breunig, H. J. Z. Naturforsch., B: Chem. Sci. 1978,
33, 242-243. (c) Breunig, H. J.; Pawlik, J. Z. Anorg. Allg. Chem.
1995, 621, 817-822. (d) Breunig, H. J.; Ro¨sler, R.; Lork, E. Z. Anorg.
Allg. Chem. 1999, 625, 1619-1623.
(10) (a) Stang, P. J.; Olenyuk, B. Acc. Chem. Res. 1997, 30, 502-518. (b)
Lindoy, L. F.; Atkinson, I. M. Self-assembly in Supramolecular
Systems; Royal Society of Chemistry: Cambridge, U.K., 2000. (c)
Fujita, M., Ed. Molecular Self-Assembly Organic Versus Inorganic
Approaches; Springer: Berlin, Germany, 2000. (d) Seidel, S. R.; Stang,
P. J. Acc. Chem. Res. 2002, 35, 972-983. (e) Keizer, H. M.; Sijbesma,
R. P. Chem. Soc. ReV. 2005, 34, 226-234.
346 Inorganic Chemistry, Vol. 45, No. 1, 2006