COMMUNICATIONS
[1] Reviews: a) R. J. Ternansky, J. M. Morin, Jr. in The Organic Chemistry
of b-Lactams (Ed.: G. I. Georg), VCH, New York, 1993, p. 2 57; b) L.
Ghosez, J. Marchand-Brynaert in Comprehensive Organic Synthesis,
Vol. 5 (Eds.: B. Trost, I. Fleming), Pergamon, Oxford, 1991, p. 85.
[2] H. Staudinger, Liebigs Ann. Chem. 1907, 356, 51.
[3] T. Kikuchi, T. Nishinaga, S. Uyeo, O. Yamashiro, K. Minami,
Tetrahedron Lett. 1968, 909.
[4] a) G. M. Salitura, C. A. Townsend, J. Am. Chem. Soc. 1990, 112, 760;
(excluding structure factors) for the structure reported in this paper
have been deposited with the Cambridge Crystallographic Data
Centre as supplementary publication no. CCDC-135522. Copies of the
data can be obtained free of charge on application to CCDC, 12Union
Road, Cambridge CB21EZ, UK (fax: (44)1223-336-033; e-mail:
deposit@ccdc.cam.ac.uk).
[18] (S)-13 had [a]2D0 À20.1 (c 0.8, CH3OH). Lit.: [a]2D0 À19.8 (c 1,
CH3OH); D. M. Floyd, A. W. Fritz, J. Pluscec, E. R. Weaver, C. M.
Cimarusti, J. Org. Chem. 1982, 47, 5160.
Â
Â
b) C. Cativiela, M. Dõaz de Villegas, J. A. Galvez, Tetrahedron:
Asymmetry 1994, 5, 1465.
[5] As a remarkable exception, N-methylene[bis(trimethylsilyl)methyl]-
amine has recently been described as a stable, monomeric compound
suitable for cycloaddition reactions with ketenes: C. Palomo, J. M.
Aizpurua, M. Legido, R. Lagarza, Chem. Commun. 1997, 233.
Â
[6] a) B. Alcaide, A. Rodrõguez-Vicente, M. A. Sierra, Tetrahedron Lett.
1998, 39, 163; b) B. Alcaide, L. Casarrubios, G. Domínguez, M. A.
Sierra, J. Org. Chem. 1994, 59, 7943; c) B. Alcaide, M. Aly, M. A.
Sierra, J. Org. Chem. 1996, 61, 8819; d) S. D. Sharma, U. Mehra, J. P. S.
Khurana, S. B. Pandhi, Synthesis 1987, 990; e) A. Arrieta, B. Lecea,
F. P. Cossío, C. Palomo, J. Org. Chem. 1987, 53, 3784.
A Highly Conductive Macrocycle-Linked
Metallophthalocyanine Polymer**
Richard P. Kingsborough and Timothy M. Swager*
Â
[7] Selected references: a) J. M. Lassaletta, R. Fernandez, Tetrahedron
Â
Lett. 1992, 33, 3691; b) D. Enders, R. Syrig, G. Raabe, R. Fernandez, C.
Phthalocyanines are among the most extensively investi-
gated chemical species because of their uses in chemical
sensors,[1] low-dimensional conductors,[2±6] nonlinear optics,[7]
liquid crystals,[8±12] as well as their utility as catalysts and
dyes.[13] Clearly, these properties are derived from the excep-
tional stability and delocalized electronic nature of the
macrocycle. The vast majority of metallophthalocyanine-
containing polymers are composed of axially connected
Gasch, J. M. Lassaletta, J. M. Llera, Synthesis 1996, 48; c) J. M.
Lassaletta, R. Fernandez, E. Martín-Zamora, E. Díez, J. Am. Chem.
Soc. 1996, 118, 7002; d) J. M. Lassaletta, R. Fernandez, E. Martín-
Zamora, C. Pareja, Tetrahedron Lett. 1996, 37, 5787; e) R. Fernandez,
E. Martín, C. Pareja, J. Vazquez, E. Díez, A. Monge, J. M. Lassaletta,
Angew. Chem. 1998, 110, 3598; Angew. Chem. Int. Ed. 1998, 37, 3428;
f) D. Enders, J. Vazquez, G. Raabe, Chem. Commun. 1999, 701.
Â
Â
Â
Â
Â
[8] The cycloaddition reaction of phenoxyketene with ketone hydrazones
to give racemic 1-amino b-lactams has been reported. Surprisingly, no
yields were included: S. D. Sharma, S. B. Pandhi, J. Org. Chem. 1990,
55, 2196.
phthalocyanines that possess conductivities (s) of 10À3
±
10À1 ScmÀ1 when oxidatively doped.[5, 14±17] These polymers,
however, cannot be exploited for catalytic applications
because of the lack of vacant coordination sites. Previous
work directed toward the preparation of one- and two-
dimensional and macrocycle-linked phthalocyanine polymers
resulted in moderately conductive (s 10À8 ± 10À2 ScmÀ1),
intractable materials that have not been studied electro-
chemically.[18±21] Electrochemical polymerization of designed
phthalocyanine macrocycles offers a number of advantages
over existing systems, including the deposition of thin electro-
active films wherein the electronic states of the macrocycle p
system mix with those of the polymer backbone. After
considering all the desirable attributes that phthalocyanine
ligands offer we chose them as ideal moieties from which to
design electroactive metal-containing polymers.[22±26] Herein
we report the synthesis of a novel highly electroactive
polythiophene ± metallophthalocyanine hybrid material that
exhibits conductivities more than three orders of magnitude
higher than previously synthesized macrocycle-connected
polymers.
[9] J. K. Whitesell, Chem. Rev. 1989, 89, 1581.
[10] In contrast with 1a ± e, hydrazone 1 f failed in the 1,2addition to
Â
trifluoromethyl ketones: C. Pareja, E. Martín-Zamora, R. Fernandez,
J. M. Lassaletta, J. Org. Chem. 1999, 64, 8846. In addition, ab initio
calculations predict an almost perfect planar geometry for the
hydrazone moiety in the transition states corresponding to the
addition of N,N-dialkylhydrazones to p-electrophiles: R. R. Pappa-
Â
Ä
lardo, J. M. Munoz, R. Fernandez, J. M. Lassaletta, unpublished
results.
[11] A. Defoin, A. Brouillard-Poichet, J. Streith, Helv. Chim. Acta 1991, 74,
103.
[12] a) S. G. Amin, R. D. Glazer, M. S. Manhas, Synthesis 1979, 210;
b) G. I. Georg, P. M. Manshava, X. Guan, Tetrahedron Lett. 1991, 32,
581.
[13] D. A. Evans, E. B. Sjogren, Tetrahedron Lett. 1985, 26, 3783.
[14] M. J. Burk, J. E. Feaster, J. Am. Chem. Soc. 1992, 114, 6266.
[15] B. S. Thyagarajan, Mechanism of Molecular Migration, Vol. 2, Wiley,
New York, 1967, p. 249.
[16] The scope and mechanistic aspects of this novel reaction are currently
under study in our laboratory.
[17] Crystal data for (R,S)-3e: Suitable crystals were obtained from Et2O/
cyclohexane at 48C. C20H27N3O6, Mr 405.45, crystal size 0.06 Â
0.18 Â 0.20 mm, orthorhombic, space group P212121, a 7.557(2), b
14.066(4), c 19.945(5) , V 2120.2(10) 3, Z 4, 1calcd
1.270 gcmÀ3, 2.508 < V< 20.798, MoKa radiation (l 0.71073 ), T
173(2) K. 3856 reflections collected, 2104 were independent [I >
2d(I)]; 266 parameters, R 0.0774 (wR 0.1291). The crystal was
mounted in a CCD diffractometer equipped with a low temperature
device and a normal focus, 2.4 kW sealed tube X-ray source operating
at 50 kV and 20 mA. Data were collected over a quadrant of the
reciprocal space by a combination of two exposure sets, using w scan
over the range 3 < q < 228. The intensities were corrected for Lorentz
and polarization effects. No absorption correction. The structure was
solved by Multan and Fourier methods. Full matrix least-square
refinement was carried out minimizing w (Fo2 À Fc22. Hydrogen atoms
were included in their calculated positions. Refinement on F 2 for all
reflections. Weighted R factors (wR) and all GOFs are based on F 2;
conventional R factors are based on F. The configuration of C-3 is
based on that known for C-2' in the auxiliary. Crystallographic data
[*] Prof. T. M. Swager, R. P. Kingsborough
Department of Chemistry and
Center for Material Science and Engineering
Massachusetts Institute of Technology
Cambridge, MA 02139 (USA)
Fax : (1)617-253-8929
[**] Funding from the Office of Naval Research is gratefully acknowl-
edged. This work was supported in part by the MRSEC Program of
the National Science Foundation under award number DMR 98 ±
08941.
Supporting information for this article is available on the WWW under
Angew. Chem. Int. Ed. 2000, 39, No. 16
ꢀ WILEY-VCH Verlag GmbH, D-69451 Weinheim, 2000
1433-7851/00/3916-2897 $ 17.50+.50/0
2897