Electronic Structures and Reactivities of CorroleϪCopper Complexes
19F NMR ([D8]toluene, 300 MHz, room temp.): δ ϭ Ϫ136.04 (s, 2
FULL PAPER
X-ray Crystallography of [Cu(tdcc)] (2a): The crystalline sample of
F, o-F), Ϫ136.98 (d, J ϭ 21.17 Hz, 2 F, o-F), Ϫ137.56 (d, J ϭ 2a was covered with a thin layer of light oil and cooled to 110 K
21.17 Hz, 2 F, o-F), Ϫ138.12 (m, 4 F, o-F), Ϫ138.62 (d, J ϭ in order to minimize the escape of the volatile crystallization sol-
21.17 Hz, 2 F, o-F), Ϫ151.62 (t, J ϭ 21.17 Hz, 2 F, p-F), Ϫ152.01 vent and minimize thermal motion/structural disorder effects. The
(dt, 4 F, p-F), Ϫ159.79 (s, 2 F, m-F), Ϫ160.81 (m, 8 F, m-F),
Ϫ163.06 (t, J ϭ 21.17 Hz, 2 F, m-F) ppm.
intensity data were corrected for absorption. The structure was
solved and refined by standard crystallographic techniques. All
non-hydrogen atoms of the corroles were refined anisotropically.
The hydrogen atoms were located in calculated positions, and were
refined using a riding model with fixed thermal parameters [Uij ϭ
1.2 Uij(eq.) for the atom to which they are bonded]. Complex 2a
crystallized as an n-heptane solvate. 2C37H17Cl6N4Cu·1/2C7H16,
Cu(tdcc) (2a) and the Dinuclear Complex 2b: A threefold excess of
Cu(OAc)2·H2O (25 mg, 0.12 mmol) was added to a solution of 2
(30 mg, 0.04 mmol) in pyridine (5 mL) in one portion and mixed
for 30 min at room temp. After solvent evaporation and column
chromatography (silica gel; n-hexane/CH2Cl2, 4:1), 2a was isolated
as a red powder (26 mg, 85% yield). X-ray quality crystals were
obtained by recrystallization from CH2Cl2/n-heptane. When an
identical reaction mixture was heated to reflux for 30 min, 2a
(15 mg, 45% yield) and 2b (14 mg, 42%% yield) were separated by
column chromatography (silica gel; n-hexane/CH2Cl2, 10:3).
¯
M ϭ 1637.68, triclinic, space group P1, a ϭ 12.3630(2), b ϭ
˚
16.5760(3), c ϭ 17.8710(4) A, α ϭ 93.615(1), β ϭ 92.401(1), γ ϭ
3
˚
97.352(1)°, V ϭ 3401.9(1) A , Z ϭ 2, T ϭ 110(2) K, Dc
ϭ
1.599 g·cmϪ3, µ(Mo-Kα) ϭ 1.15 mmϪ1, 15035 unique reflections
to 2θmax ϭ 56.6°, 902 refined parameters, R1 ϭ 0.055 for 120571
observations with I Ͼ 2σ(I), R1 ϭ 0.096 (wR2 ϭ 0.108) for all
unique data, ∆ρ Յ 0.64 e/A . The asymmetric unit consists of two
corrole species and half of the n-heptane solvate molecule which is
3
˚
2a: UV/Vis (benzene): λmax (ε ϫ 10Ϫ4) ϭ 406 (4.71), 548 (0.56) nm.
MS (DCIϪ): m/z (%) ϭ 794 (100) [MϪ]. 1H NMR (toluene,
500 MHz, room temp.): δ ϭ 7.69 (br. s, 2 H), 7.26 (br. s, 2 H), 7.17
(br. s, 2 H), 6.86 (unresolved d, 2 H), 7.10 (d, J ϭ 8 Hz, 4 H, m-
H), 7.04 (d, J ϭ 8 Hz, 2 H, m-H), 6.68 (t, J ϭ 8.25 Hz, 2 H, p-H),
6.63 (t, J ϭ 8.25 Hz, 1 H, p-H) ppm. 1H NMR (toluene, 500 MHz,
240 K): δ ϭ 7.43 (d, J ϭ 4.37 Hz, 2 H), 7.19 (d, J ϭ 4.37 Hz, 2
H), 7.01 (d, J ϭ 4.77 Hz, 2 H), 6.97 (d, J ϭ 4.77 Hz, 2 H), 6.92 (d,
J ϭ 8.34 Hz, 4 H, m-H), 6.83 (d, J ϭ 8.34 Hz, 2 H, m-H), 6.56 (t,
J ϭ 8.25 Hz, 2 H, p-H), 6.50 (t, J ϭ 8.25 Hz, 1 H, p-H) ppm.
located on, and disordered about,
a center of inversion.
CCDC-206173 contains the supplementary crystallographic data
for this paper. These data can be obtained free of charge at
www.ccdc.cam.ac.uk/conts/retrieving.html [or from the Cambridge
Crystallographic Data Centre, 12 Union Road, Cambridge
CB2 1EZ, UK; Fax: (internat.)
deposit@ccdc.cam.ac.uk].
ϩ 44-1223/336-033; E-mail:
2b: UV/Vis (benzene): λmax (ε ϫ 10Ϫ4) ϭ 410 (12.8), 560 (2.14)
Acknowledgments
1
nm. MS (DCIϪ): m/z (%) ϭ 1584 (100) [MϪ]. H NMR (toluene,
This research was supported by the Israel Science Foundation un-
der Grants 368/00 (Z. G.) and 68/01 (I. G.). A postdoctoral fellow-
ship for L. S. by the Institute of Catalysis Science and Technology
of the Technion is acknowledged as well.
500 MHz, room temp.): δ ϭ 7.77 (br. s, 4 H), 7.64 (br. s, 4 H), 6.86
(d, J ϭ 4 Hz, 4 H), 6.53 (unresolved d, 4 H), 7.19 (unresolved d, 6
H, m-H), 7.06 (unresolved d, 4 H, m-H), 6.67 (d, J ϭ 8 Hz, 2 H,
m-H), 6.68 (t, J ϭ 8 Hz, 2 H, p-H), 6.58 (t, J ϭ 8.25 Hz, 2 H, p-
H), 6.40 (t, J ϭ 8 Hz, 2 H, p-H) ppm. 1H NMR (toluene, 500 MHz,
235 K): δ ϭ 7.38 (br. s, 2 H), 7.33 (d, J ϭ 3.97 Hz, 2 H), 7.26 (d,
J ϭ 3.97 Hz, 2 H), 6.85 (d, J ϭ 4.37 Hz, 2 H), 6.73 (d, J ϭ 4.77 Hz,
2 H), 6.44 (unresolved d, 2 H), 7.01 (unresolved d, 2 H), 6.98 (m,
6 H, m-H), 6.79 (m, 6 H, m-H), 6.54 (t, J ϭ 8 Hz, 2 H, p-H), 6.54
[1]
For reviews that cover the chemistry of corrole up to 1999,
[1a]
see:
J. L. Sessler, S. J. Weghorn, in Expanded, Contracted &
[1b]
Isomeric Porphyrins, Pergamon, Oxford, 1997, pp. 11Ϫ85.
R. Paolesse, in The Porphyrin Handbook, vol. 2 (Eds.: K. M.
Kadish, K. M. Smith, R. Guilard), Academic Press, New York,
1
(t, J ϭ 8.25 Hz, 2 H, p-H), 6.25 (t, J ϭ 8 Hz, 2 H, p-H) ppm. H
[1c]
2000, chapter 11, pp. 201Ϫ231.
K. M. Kadish, in The Por-
NMR (toluene, 500 MHz, 320 K): δ ϭ 8.06 (br. s, 2 H), 7.86 (br.
s, 2 H), 7.42 (br. s, 2 H), 7.38 (br. s, 2 H), 7.15 (br. s, 2 H), 6.86
(br. s, 2 H), 6.39 (br. s, 2 H), 7.32 (d, J ϭ 7.9 Hz, 6 H, m-H), 7.23
(d, J ϭ 7.8 Hz, 6 H, m-H), 6.72 (t, J ϭ 8.07 Hz, 2 H, p-H), 6.63
(t, J ϭ 8.07 Hz, 2 H, p-H), 6.45 (t, J ϭ 8.07 Hz, 2 H, p-H) ppm.
phyrin Handbook, vol. 2 (Eds.: K. M. Kadish, K. M. Smith, R.
Guilard), Academic Press, New York, 2000, chapter 12, pp.
233Ϫ295.
[2]
For only the two triarylcorroles that were reported prior to
[2a]
1999, see:
N. M. Loim, E. V. Grishko, N. I. Pyshnograeva,
E. V. Vorontsov, V. I. Sokolov, Izv. Akad. Nauk. Ser. Khim.
[2b]
Chemical Oxidation of [Cu(tdcc)] (2a): Solid (BrC6H4)3NSbCl6
(13 mg, 18 µmol) was added in one portion to a well-stirred solu-
tion of 2a (5 mg, 6 µmol) in CH2Cl2. The color changed to yellow-
green within a few minutes, after which the solution was filtered
and used for the spectroscopic examinations.
1994, 5, 925.
E. Rose, A. Kossanyi, M. Quelquejeu, M.
Soleilhavoup, F. Duwavran, N. Bernard, A. Lecas, J. Am.
Chem. Soc. 1996, 118, 1567.
[3] [3a]
Z. Gross, N. Galili, I. Saltsman, Angew. Chem. Int. Ed.
1999, 38, 1427. [3b] Z. Gross, N. Galili, L. Simkhovich, I. Salts-
man, M. Botoshansky, D. Bläser, R. Boese, I. Goldberg, Org.
Lett. 1999, 1, 599. [3c] L. Simkhovich, I. Goldberg, Z. Gross, J.
Chemical Reduction of [Cu(tdcc)] (2a): A saturated solution of
Na2S2O4 (2 mg, 0.011 mmol) in H2O (2 mL) was added in one por-
tion to a 50-mL three-necked, round-bottomed flask containing a
solution of 2a (5 mg, 6 µmol) in ethanol (2 mL). The mixture was
stirred under Ar for 5 min, during which time the color changed
from red to green. This solution was used for the EPR measure-
ments, still under Ar.
[3d]
Inorg. Biochem. 2000, 80, 235.
E. Steene, T. Wondimagegn,
A. Ghosh, J. Inorg. Biochem. 2002, 88, 113. [3e] L. Simkhovich,
[3f]
I. Goldberg, Z. Gross, Org. Lett. 2003, 5, 1241.
J. P.
[3g]
Collman, R. A. Decreau, Tetrahedron Lett. 2003, 44, 1207.
D. T. Gryko, B. Koszarna, Org. Biomol. Chem. 2003, 1, 350.
[4] [4a]
R. Paolesse, L. Jaquinod, D. J. Nurco, S. Mini, F. Sagone,
[4b]
T. Boschi, K. M. Smith, Chem. Commun. 1999, 1307.
R.
Paolesse, S. Nardis, F. Sagone, R. G. Khoury, J. Org. Chem.
2001, 66, 550.
Electrochemistry: The cyclovoltammograms of the complexes were
measured for approximately 0.5 m substrate in 0.05 TBAP/
C6H5CN solutions at scan rates of 100 V/s with Ag/AgCl reference
electrode. The redox potentials are reported vs. the ferrocene/ferro-
cenium redox couple observed at 0.4 V vs. Ag/AgCl.
[5] [5a]
[5b]
J.-W. Ka, C.-H. Lee, Tetrahedron Lett. 2000, 41, 4609.
J.-W. Ka, W.-S. Cho, C.-H. Lee, Tetrahedron Lett. 2000, 41,
[5c]
[5d]
[5e]
8121.
D. T. Gryko, Chem. Commun. 2000, 2243.
D. T.
R. P.
Gryko, K. Jadach, J. Org. Chem. 2001, 66, 4267.
Eur. J. Inorg. Chem. 2004, 1724Ϫ1732
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
1731