Angewandte
Chemie
ꢀ
1999, 38, 1512; d) P. J. Sadler, H. Li, H. Sun, Coord. Chem. Rev.
1999, 185–186, 689.
[4] N. Ya. Turova, Russ. Chem. Rev. 2004, 73, 1041.
[5] J. H. Thurston, D. C. Swenson, L. Messerle, Chem. Commun.
2005, 4228.
individual Bi O bond lengths and Bi-O-Bi bond angles show
some significant deviations.
Aggregation of the bismuth oxido cluster occurs on
dissociation of [Bi(hfac)3] from 1 according to Equation (2).
[6] K. H. Whitmire, S. Hoppe, O. Sydora, J. L. Jolas, C. M. Jones,
Inorg. Chem. 2000, 39, 85.
[7] L. Liu, L. N. Zakharov, A. L. Rheingold, T. A. Hanna, Chem.
Commun. 2004, 1472.
45 ½Bi9O7ðhfacÞ13 ! 7 ½Bi38O45ðhfacÞ24 ð2Þ þ 139 ½BiðhfacÞ3
ð2Þ
Integration of the NMR spectrum in THF gave a proton
ratio for 2:[Bi(hfac)3] of 29.8:70.2 (the theoretical value is
28.7:71.3). Such ligand redistribution in polar solvents is a
well-known phenomenon[17] for heteroleptic metal b-diketo-
nates. While 2 is insoluble in noncoordinating and aromatic
solvents, the striking feature of this giant molecule is its
solubility without decomposition in coordinating solvents
such as acetone, THF, acetonitrile, DMSO, alcohols, and
diethyl ether. Oxido diketonate 2 can be recrystallized from
these solutions, for which both 1H and 19F NMR spectra show
single peaks (Figure 2e,f), and the mass spectrum is similar to
that shown in Figure 3b.
In conclusion, we have demonstrated that a fluorinated
tetraol indeed functions as a source of both diketonate and
oxido groups in the presence of a base acting as an irreversible
proton sink. This synthetic pathway has been confirmed by
the isolation of the first bismuth oxido diketonate [Bi9O7-
(hfac)13] in quantitative yield. Our preliminary results indicate
that oxido diketonates of other metals can be obtained by this
approach. Importantly, the technique can also be applied to
the synthesis of heterometallic oxido diketonates that are
immediate precursors for functional oxide materials. We
found that in coordinating solvents the nonanuclear oxido
diketonate undergoes dissociation of [Bi(hfac)3] followed by
aggregation into the giant oxido cluster [Bi38O45(hfac)24]. The
latter could serve as a model for studying the chemistry of
bismuth oxide nanoparticles. Moreover, the assembly of this
molecule shows the way for construction of other nanosized
oxido clusters of metals that exhibit a similar coordination
environment in their oxido compounds, such as lead and the
lanthanides.
[8] a) D. Mansfeld, M. Mehring, M. Schürmann, Angew. Chem.
2005, 117, 250; Angew. Chem. Int. Ed. 2005, 44, 245; b) M.
Mehring, D. Mansfeld, S. Paalasmaa, M. Schürmann, Chem. Eur.
J. 2006, 12, 1767.
[9] V. V. Sharutin, I. V. Egorova, O. K. Sharutina, T. K. Ivanenko,
N. Yu. Adonin, V. F. Starichenko, M. A. Pushilin, A. V. Gerasi-
menko, Russ. J. Coord. Chem. 2005, 31, 2.
[10] M. Mehring, M. Schürmann, Chem. Commun. 2001, 2354.
[11] a) J. W. Pell, W. C. Davis, H. C. zur Loye, Inorg. Chem. 1996, 35,
5754; b) S. Parola, R. Papiernik, L. G. Hubert-Pfalzgraf, S.
Jagner, M. Hakansson, J. Chem. Soc. Dalton Trans. 1997, 4631;
c) S. Parola, R. Papiernik, L. G. Hubert-Pfalzgraf, C. Bois, J.
Chem. Soc. Dalton Trans. 1998, 737; d) J. H. Thurston, K. H.
Whitmire, Inorg. Chem. 2003, 42, 2014; e) M. Mehring, S.
Paalasmaa, M. Schürmann, Eur. J. Inorg. Chem. 2005, 4891.
[12] C. D. Chandler, C. Roger, M. J. Hampden-Smith, Chem. Rev.
1993, 93, 1205.
[13] a) U. Schubert, J. Mater. Chem. 2005, 15, 3701; b) L. G. Hubert-
Pfalzgraf, H. Guillon, Appl. Organomet. Chem. 1998, 12, 221;
c) T. Kemmitt, M. Daghish, Inorg. Chem. 1998, 37, 2063; d) F.
Ribot, P. Toledano, C. Sanchez, Chem. Mater. 1991, 3, 759.
[14] U. Schubert, Chem. Mater. 2001, 13, 3487.
[15] E. Bouwman, K. G. Caulton, G. Christou, K. Folting, C. Gasser,
D. N. Hendrickson, J. C. Huffman, E. B. Lobkovsky, J. D. Martin,
P. Michel, H.-L. Tsai, Z. Xue, Inorg. Chem. 1993, 32, 3463.
[16] X-ray crystal data for 1: Bi9C65H13F78O33, Mr = 4684.57, mono-
clinic, P21/c, a = 16.7517(8), b = 25.4542(11), c = 26.0444(12) ,
b = 96.8500(10)8,
Bi38C120H24F144O93, Mr = 13630.63, monoclinic, P21/n, a =
20.4459(12), b = 28.3746(16), c = 21.3740(12) , b =
V= 11026.1(9) 3,
Z = 4.
For
2:
93.3470(10)8, V= 12378.9(12) 3, Z = 2. See Supporting Infor-
mation for more details. CCDC 604688 and 604689 (1 and 2)
contain the supplementary crystallographic data for this paper.
These data can be obtained free of charge from The Cambridge
request/cif.
[17] a) J. H. Wengrovius, M. F. Garbauskas, E. A. Williams, R. C.
Going, P. E. Donahue, J. F. Smith, J. Am. Chem. Soc. 1986, 108,
982; b) V. G. Kessler, S. Gohil, S. Parola, Dalton Trans. 2003, 544.
Received: April 28, 2006
Revised: May 25, 2006
Published online: July 26, 2006
Keywords: bismuth · cluster compounds · O ligands ·
.
oxido ligands
[1] a) L. G. Hubert-Pfalzgraf, J. Mater. Chem. 2004, 14, 3113;
b) L. G. Hubert-Pfalzgraf, Inorg. Chem. Commun. 2003, 6, 102;
c) V. G. Kessler, Chem. Commun. 2003, 1213; d) N. Ya. Turova,
E. P. Turevskaya, V. G. Kessler, M. I. Yanovskaya, J. Sol-Gel Sci.
Technol. 1994, 2, 17.
[2] a) G. Fornasieri, L. Rozes, S. Le Calve, B. Alonso, D. Massiot,
M. N. Rager, M. Evain, K. Boubekeur, C. Sanchez, J. Am. Chem.
Soc. 2005, 127, 4869; b) U. Schubert, J. Sol-Gel Sci. Technol.
2004, 31, 19; c) F. R. Kogler, M. Jupa, M. Puchberger, U.
Schubert, J. Mater. Chem. 2004, 14, 3133.
[3] a) K. H. Thompson, C. Orvig, Science 2003, 300, 936; b) G. G.
Briand, N. Burford, Chem. Rev. 1999, 99, 2601; c) Z. Guo, P. J.
Sadler, Angew. Chem. 1999, 111, 1610; Angew. Chem. Int. Ed.
Angew. Chem. Int. Ed. 2006, 45, 5448 –5451ꢀ 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
5451