Angewandte
Chemie
[5] E. Vogel, M. Michels, L. Zander, J. Lex, N. S. Tuzum, K. N.
ions on the opposite hemi-macrocycle with their pyrrolic b-
fluorine atoms close to the silver ion, while the pentafluoro-
phenyl substituents at the meso positions between pyrroles D
and E and between pyrroles A and H also lie close to the
silver ions. These structural features lead to through-space
coupling of the related fluorine atoms with silver ions.[15] The
Houk, Angew. Chem. 2003, 115, 2964; Angew. Chem. Int. Ed.
2003, 42, 2857.
[6] Y. Tanaka, W. Hoshino, S. Shimizu, K. Youfu, N. Aratani, N.
Maruyama, S. Fujita, A. Osuka, J. Am. Chem. Soc. 2004, 126,
3046.
[7] S. Shimizu, J.-Y. Shin, H. Furuta, R. Ismael, A. Osuka, Angew.
Chem. 2003, 115, 82; Angew. Chem. Int. Ed. 2003, 42, 78.
[8] Crystal data for 5: C88H4F56N8O3Cu2, MW = 2412.07, monoclinic,
space group P21/n (no. 14), a = 17.7961(14), b = 23.5392(18), c =
À
Ag N bond distances are in the range of 2.27–2.40 ꢀ. We thus
assigned complex 9 as a disilver(i) complex of perfluorinated
[34]octaphyrin.
22.4783(17) ꢀ, b = 92.598(2)8, V= 9406.6(13) ꢀ3, Z = 4, 1calcd
=
Despite the figure-of-eight structures that are similar to
that of 2, both disilver complexes 8 and 9 are thermally stable
and do not exhibit any splitting reactivity, as observed for 2. A
major reason for the absence of thermal splitting reactivity
may be the 34-p-electron systems of 8 and 9 which rationally
preclude splitting into two 18-p-electron porphyrins. We thus
attempted the reduction of 8 and 9 with NaBH4 which caused
spontaneous demetalation of the complexes to provide the
respective free-base [38]octaphyrins.
1.703 gcmÀ3, T= À1538C. R = 0.0648, Rw = 0.1731 (all data),
GOF = 0.972 (I > 2s(I)).
[9] In the temperature range 20–2 K, the susceptibility value slightly
decreased (cpT= 0.70 emuKmolÀ1 at 2 K), which can be
accounted for in terms of weak antiferromagnetic coupling of
the two copper(ii) ions (J = À0.306 cmÀ1, g = 2.110) despite the
long separation (5.41 ꢀ). See Supporting Information.
[10] Differential scanning calorimetry (DSC) measurement on 6
revealed sharp exothermic responses around 170–2008C (see
Supporting Information).
In summary, metalation of the perfluorinated octaphyrin 4
with copper resulted in the formation of the dicopper complex
5 with an unprecedented concomitant hydrolytic ring opening
of one of the pyrrole units. The octaphyrin framework was
restored by demetalation with TFA and H2SO4. In contrast,
metalation of both octaphyrin 1 and 4 with silver proceeded
with initial two-electron oxidation of the ligands to give
twisted figure-of-eight disilver(i) complexes of [34]octaphyr-
ins that are thermally very stable. The structures and proper-
ties of dimetal complexes of octaphyrins are diverse and
depend on the individual properties of the metal ion and the
ligand, and they hail great potential for expanded porphyrins,
which are actively pursued in our laboratory.
[11] Crystal data for 8: C114H28F50N10Ag2O7, MW = 2815.19, triclinic,
¯
space group P1 (no. 2), a = 15.908(8), b = 15.978(7), c =
21.28(1) ꢀ, a = 99.02(4), b = 94.61(4), g = 106.71(4)8, V=
5071(4) ꢀ3, Z = 2, 1calcd = 1.843 gcmÀ3, T= À1508C. R = 0.092,
Rw = 0.253 (all data), GOF = 1.298 (I > 2s(I)).
[12] a) W. R. Scheidt, J. U. Mondal, C. W. Eigenbrot, A. Adler, L. J.
Radonovich, J. L. Hoard, Inorg. Chem. 1986, 25, 795; b) H.
Furuta, T. Ogawa, Y. Uwatoko, K. Araki, Inorg. Chem. 1999, 38,
2676; c) C. Brꢁcker, C. A. Barta, R. P. Brinas, J. A. Krause
Bauer, Inorg. Chem. 2003, 42, 1673.
[13] Similar through-space coupling of the protons of a p-phenylene
´
moiety with cadmium(ii) ions was reported, see: a) M. Ste˛pien,
´
L. Latos-Graz˙ynski, J. Am. Chem. Soc. 2002, 124, 3838; b) M.
´
´
Ste˛pien, L. Latos-Graz˙ynski, Acc. Chem. Res. 2005, 38, 88.
[14] Crystal data for 9: C90H2F56N8Cl2Ag2O3, MW = 2593.61, triclinic,
¯
space group P1 (no. 2), a = 14.820(2), b = 17.797(2), c =
Received: February 23, 2005
Revised: March 22, 2005
Published online: May 11, 2005
19.159(3) ꢀ, a = 67.010(2), b = 87.229(2), g = 66.519(2)8, V=
4232.2(10) ꢀ3, Z = 2, 1calcd = 2.035 gcmÀ3
,
T= À1838C. R =
0.061, Rw = 0.117 (I > 3s(I)), GOF = 0.945. CCDC-264267 (5),
264268 (9), and 264302 (8) contain the supplementary crystallo-
graphic data for this paper. These data can be obtained free of
charge from the Cambridge Crystallographic Data Centre via
Keywords: copper · macrocycles · porphyrinoids · silver
.
[15] Selected signals of the b-, o-, and m-fluorine atoms were coupled
with AgI ions probably as a result of through-space interactions
(see Supporting Information).
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Angew. Chem. Int. Ed. 2005, 44, 3726 –3729
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