COMMUNICATIONS
[
[
1] a) R. Noyori, Asymmetric Catalysis in Organic Synthesis, Wiley, New
York, 1994; b) T. Ohkuma, M. Kitamura, R. Noyori in Catalytic
Asymmetric Synthesis (Ed.: I. Ojima), Wiley-VCH, Weinheim, 2000,
p. 1; c) J. M. Brown in Comprehensive Asymmetric Catalysis (Eds.:
E. N. Jacobsen, A. Pfaltz, H. Yamamoto), Springer, Berlin, 1999,
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[18] a) M. J. Burk, Y. M. Wang, J. R. Lee, J. Am. Chem. Soc. 1996, 118,
5142; b) M. J. Burk, G. Casy, N. B. Johnson, J. Org. Chem. 1998, 63,
6084; c) G. Zhu, X. Zhang, J. Org. Chem. 1998, 63, 9590; d) I. D.
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Angew. Chem. Int. Ed. 2002, 41, 1612.
V
I
A Remarkable 14-Nuclear Re Ag
8
6
Coordination Oligomer Derived from a 2D
Re Ag ) Coordination Polymer with
3
064.
3] a) M. H. Wu, K. B. Hansen, E. N. Jacobsen, Angew. Chem. 1999, 111,
167; Angew. Chem. Int. Ed. 1999, 38, 2012; b) A. G. Dossetter, P. F.
V
I
(
[
2
2 n
2
d-Penicillaminate
Jamison, E. N. Jacobsen, Angew. Chem. 1999, 111, 2549; Angew.
Chem. Int. Ed. 1999, 38, 2398; c) M. S. Sigman, E. N. Jacobsen, J. Am.
Chem. Soc. 1998, 120, 5315; d) W. Zhang, J. L. Loebach, S. R. Wilson,
E. N. Jacobsen, J. Am. Chem. Soc. 1990, 112, 2801.
Takumi Konno,* Yuichi Shimazaki,
Tadashi Yamaguchi, Tasuku Ito, and
Masakazu Hirotsu
[
[
4] H. Nishiyama, Enantiomer 1999, 4, 569.
5] a) M. J. Burk, J. Am. Chem. Soc. 1991, 113, 8518; b) M. J. Burk, J. E.
Feaster, W. A. Nugent, R. L. Harlow, J. Am. Chem. Soc. 1993, 115,
There has been considerable interest in the design and
creation of metallo-supramolecular systems that exhibit
unique structural and chemical properties.[ In many cases,
metallo-supramolecular structures have been constructed
from organic multidentate ligands and metal ions through
self-assembly processes. Our synthetic strategy involves the
use of octahedral metal complexes containing relatively
simple thiolate ligands, such as 2-aminoethanethiolate (aet),
1
0125.
1]
[
6] a) A. Togni, R. L. Halterman, Metallocenes, Vol. 2, Wiley-VCH,
Weinheim, 1998, pp. 685 ± 721; b) C. J. Richards, A. Locke, Tetrahe-
dron: Asymmetry 1998, 9, 2377; c) A. Togni, N. Bieler, U. Burckhardt,
C. Kollner, G. Pioda, R. Schneider, A. Schnyder, Pure Appl. Chem.
1
999, 71, 1531; d) C. Bolm, K. Muniz, J. P. Hildebrand, Org. Lett. 1999,
1, 491.
[
[
[
7] a) T. Ireland, G. Grossheimann, C. Wieser-Jeunesse, P. Knochel,
Angew. Chem. 1999, 111, 3397; Angew. Chem. Int. Ed. 1999, 38, 3212;
b) T. Ireland, K. Tappe, G. Grossheimann, P. Knochel, Chem. Eur. J.
l-cysteinate (l-cys), and d-penicillaminate (d-pen; d-H pen ¼
2
d-penicillamine), as building blocks that are aggregated by
forming S-bridged structures with metal ions.[ This method
allows the construction of well-organized heterometallic
aggregates which have several chiral centers by a systematic
variation and combination of metal ions with different
coordination geometries. For example, a number of chiral S-
2
002, 8, 843.
2±5]
8] For reviews see: a) K. E. Koenig, Asymmetric Synthesis, Vol 5 (Ed.:
J. D. Morrison), Academic Press, Orlando, FL, 1985, p. 71 ±101; b) H.
Takaya, T. Ohta, R. Noyori, Catalytic Asymmetric Synthesis (Ed.: I.
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9] M.J. Burk, M. F. Gross, T. G. Harper, C. S. Kalberg, J. R. Lee, J. P.
Martinez, Pure Appl. Chem. 1996, 68, 37.
III
II
I
[
[
[
10] The new ligands were patented in collaboration with Degussa AG: M.
Lotz, P. Knochel, A. Monsees, T. Riermeier, R. Kadyrov, J. J. Almena
Perea, Ger. Pat. No. DE 10219490.
11] a) D. Guillaneux, H. B. Kagan, J. Org. Chem. 1995, 60, 2502; b) O.
Riant, G. Argouarch, D. Guillaneux, O. Samuel, H. B. Kagan, J. Org.
Chem. 1998, 63, 3511.
bridged aggregates, which include Co Pd M octanuclear
4 2 2
I
II
III
6þ
[2e]
metallacycles [M {Pd [Co (aet) ] } ] (M ¼ Ag, Au), have
2
3 2 2
III
been prepared just from [Co (aet) ] and appropriate metal
3
ions.[
2]
While it has been established that thiolato groups coordi-
II
III
12] CCDC 189275 contains the supplementary crystallographic data for
this paper. These data can be obtained free of charge via www.ccdc.ca-
m.ac.uk/conts/retrieving.html (or from the Cambridge Crystallo-
graphic Data Centre, 12, Union Road, Cambridge CB21EZ, UK;
fax: (þ 44)1223-336-033; or deposit@ccdc.cam.ac.uk).
nated to an M or M metal center have the ability to bind to
[2±6]
a second metal ion to form S-bridged structures,
the
coordinating ability of thiolato groups bound to a metal center
with a higher oxidation state has not been widely investigat-
ed.[ In fact, S-bridged heterometallic aggregates based on
7]
[
[
13] A typical procedure for the synthesis of diphosphane 2 is described in
the Supporting Information.
14] a) A. Togni, C. Breutel, A. Schnyder, F. Spindler, H. Landert, A.
Tijani, J. Am. Chem. Soc. 1994, 116, 4062; b) M. J. Burk, J. R. Lee, J. P.
Martinez, J. Am. Chem. Soc. 1994, 116, 10847; c) K. Junge, G. Oehme,
A. Monsees, T. Riermeier, U. Dingerdissen, M. Beller, Tetrahedron
Lett. 2002, 43, 4977.
15] a) M. J. Burk, F. Bienewald, M. Harris, A. Zanotti-Gerosa, Angew.
Chem. 1998, 110, 2034; Angew. Chem. Int. Ed. 1998, 37, 1931; b) J.
Holz, M. Quirmbach, U. Schmidt, D. Heller, R. St¸rmer, A. Bˆrner, J.
Org. Chem. 1998, 63, 8031.
[
*] Prof. T. Konno, Y. Shimazaki
Department of Chemistry
Graduate School of Science
Osaka University
Toyonaka, Osaka 560-0043 (Japan)
Fax : (þ 81)6-6850-5765
[
[
[
E-mail: konno@ch.wani.osaka-u.ac.jp
Dr. T. Yamaguchi, Prof. T. Ito
Department of Chemistry
Graduate School of Science
Tohoku University
16] a) M. D. Fryzuk, B. Bosnich, J. Am. Chem. Soc. 1978, 100, 5491;
b) M. J. Burk, C. S. Kalberg, A. Pizzano, J. Am. Chem. Soc. 1998, 120,
4
345; c) M. Lotz, T. Ireland, J. J. Almena Perea, P. Knochel,
Sendai, Miyagi 980-8578 (Japan)
Tetrahedron: Asymmetry 1999, 10, 1839.
17] a) J. P. GenÜt, C. Pinel, S. Mallart, S. Jugÿ, S. Thorimbert, J. A.
Laffitte, Tetrahedron: Asymmetry 1991, 2, 555; b) J. P. GenÜt, C. Pinel,
V. Ratovelomanana-Vidal, S. Mallart, X. Pfister, L. Bischoff, S.
Darses, C. Galopin, J. A. Laffitte, Tetrahedron: Asymmetry 1994, 5,
Dr. M. Hirotsu
Department of Chemistry
Faculty of Engineering
Gunma University
6
75.
Kiryu, Gunma 376-8515 (Japan)
Angew. Chem. Int. Ed. 2002, 41, No. 24
¹ 2002 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
0044-8249/02/4124-4711 $ 20.00+.50/0
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