Metallocorroles
1041±1055
3
been consumed. The reaction mixture was cooled to 258C, filtered, and the
solvent was evaporated. Purification of the material was achieved by
column chromatography (silica gel, n-hexane/EtOAc 100:1, only one
significant fraction), and a brilliant green solid material was obtained after
evaporation of the solvent. The material was recrystallized from benzene
and n-heptane. The average yield of pure 12a from several syntheses was
J(F,F) 20.0 Hz, 3F; para-F), � 161.3 (m, 6F; para-F); UV/Vis (CH
2 2
Cl ):
�
4
l
max (e  10 ): 394 (6.0), 410 (17.1), 562 (1.9), 576 nm (2.1); MS (DCI ):
m/z (%): 903.0 (100) [MH] , 867.0 (65) [MH � Cl] .
Synthesis of [Ge(tpfc)OH] (7b): Compound 7a (20 mg, 22.2 mmol) was
passed through a column of silica with CH
lization from hexane/CH Cl 7b was obtained as red crystals in 83% yield
14.7 mg, 16.6 mmol). 1H NMR (200 MHz, [D
]benzene): d 9.2 (d,
J(H,H) 4.4 Hz, 2H; b-pyrrole H), 8.8 (d, J(H,H) 4.8 Hz, 2H; b-
2 2
Cl as eluent. After recrystal-
2
2
5
5 ± 60%. 1H NMR (200 MHz, CDCl
3
): d 8.30 (unresolved d, 1H; b-
(
6
3
pyrrole H), 8.18 (d, J(H,H) 4.39 Hz, 1H; b-pyrrole H), 8.02 (d,
3
3
3
J(H,H) 4.45 Hz, 1H; b-pyrrole H), 7.93 (m, 2H), 7.86 (unresolved d,
19
pyrrole H), 8.6 (m, 4H; b-pyrrole H), � 5.1 (brs, 1H; OH); F NMR
3
1
H; b-pyrrole H), 7.76 (d, J(H,H) 4.25 Hz, 1H; b-pyrrole H), 7.60 (d,
3
4
(
8
188 MHz, [D
6
]benzene): d � 137.3 (dd, J(F,F) 21.0 Hz, J(F,F)
3
3
J(H,H) 4.17 Hz, 1H; b-pyrrole H), 6.77 (t, J(H,H) 6.30 Hz, 3H; para-
3
4
.0 Hz, 2F; ortho-F), � 1337.5 (dd, J(F,F) 25.0 Hz, J(F,F) 8.0 Hz, 1F;
3
4
H, PPh
PPh
3
), 6.58 (td, J(H,H) 7.28 Hz, J(H,H) 2.56 Hz, 6H; meta-H,
3
4
ortho-F), � 138.3 (dd, J(F,F) 25.2 Hz, J(F,F) 8.0 Hz, 1F; ortho-F),
3
22
3
3
), 6.24 (t, J(H,H) 7.67 Hz, 1H; para-H, N -aryl), 6.09 (t, J(H,H)
138.5 (dd, 3J(F,F) 23.9 Hz, 4J(F,F) 8.0 Hz, 2F; ortho-F), � 151.9 (t,
�
2
2
3
4
7
8
.67 Hz, 2H; meta-H, N -aryl), 5.82 (dd, J(H,H) 11.14 Hz, J(H,H)
3
3
J(F,F) 22.5 Hz, 1F; para-F), � 152.0 (t, J(F,F) 21.2 Hz, 2F; para-F),
3
22
.60 Hz, 6H; ortho-H, PPh
3
), 3.71 (d, J(H,H) 7.40 Hz, 2H; ortho-H, N -
3 22
�
161.3 (m, 3F; meta-F), � 162.0 (m, 3F; meta-F); UV/Vis (CH
2 2
Cl ): lmax
aryl), 1.34 (s, 1H; NH), � 4.60 (d, J(H,H) 15.02 Hz, 1H; N -benzyl),
� 4
(
(
e  10 ): 386 (3.8), 410 (20.7), 560 (1.7), 576 nm (1.5); MS (DCI ): m/z
�
3
22
19
�
5.59 (d, J(H,H) 14.89 Hz, 1H; N -benzyl); F NMR (188 MHz,
%): 883.4 (80) [M � H] , 867.0 (100) [M � OH] ; MS (DCI ): m/z (%):
3
4
CDCl
3
): d � 137.21 (dd, J(F,F) 25.00 Hz, J(F,F) 7.33 Hz, 1F; ortho-
�
8
84.2 (100) [M] .
3
3
F), � 137.67 (d, J(F,F) 24.82 Hz, 1F; ortho-F), � 138.59 (dd, J(F,F)
4
X-ray crystallography of 5e, 5c, and 12a: X-ray quality crystals of these
complexes were obtained by slow recrystallization from mixtures of
acetonitrile/n-heptane, diethyl ether/n-heptane (in the presence of pyr-
idine), and benzene/n-heptane, respectively. The diffraction data were
collected on a Nonius KappaCCD diffractometer with MoKa (l 0.7107 )
2
0.68 Hz, J(F,F) 9.15 Hz, 1F; ortho-F), � 139.91 (m, 2F; ortho-F),
3
4
�
141.89 (dd, J(F,F) 23.50 Hz, J(F,F) 5.64 Hz, 1F; ortho-F), � 152.95
3 3
(
t, J(F,F) 22.00 Hz, 1F; para-F), � 153.33 (t, J(F,F) 21.24 Hz, 1F;
3
3
para-F), � 153.84 (t, J(F,F) 21.81 Hz, 1F; para-F), � 161.64 (td, J(F,F)
4
2
2.94 Hz, J(F,F) 6.96 Hz, 1F; meta-F), � 162.48 (m, 2F; meta-F),
[
38]
�
4
radiation and reduced to intensities by DENZO. The crystal structures
were solved by a combination of Patterson and direct methods (DIRDIF-
�
163.32 (m, 3F; meta-F); UV/Vis (CH
2
Cl
2
): lmax (e  10 ) 466 (8.4),
6
14 nm (1.7). MS (DCI ): m/z (%): 1279.1 (100) [MH] , 1159 (12)
[
39, 40]
and refined by full-matrix least-squares on F 2
3
] ;
96 and SIR-92)
(SHELXL-97).
(
[
MH � C
7
H
7
� CO � H] , 897.2 (16) [MH � C
7
H
7
� CO � H � PPh
[
41]
�
�
All non-hydrogen atoms were treated anisotropically
MS (DCI ): m/z (%): 1278.2 (100) [M] , 100%).
expect for atoms of the partly disordered molecules of the respective
2
Synthesis of [Sn(tpfc)Cl] (8): A solution of 4 (25 mg, 31.4 mmol) and SnCl ´
crystallization solvents, which were refined in an isotropic manner). The
hydrogen atoms were located in calculated positions to correspond to
standard bond lengths and angles, the methyl substituents were treated as
rigid groups. The small size of the crystals and their solvent content dictated
low-temperature measurements in order to enhance their diffraction.
Crystallographic data (excluding structure factors) for the structures
reported in this paper have been deposited with the Cambridge Crystallo-
graphic Data Centre as supplementary publication no. CCDC-147594 (5e),
CCDC-147594 (5c), and CCDC-147596 (12a). Copies of the data can be
obtained free of charge on application to CCDC, 12 Union Road,
Cambridge CB21EZ, UK (fax: (44)1223-336-033; e-mail: deposit@
ccdc.cam.ac.uk). The selected crystallographic data for the analyzed
structures are:
2
3
H
2
O (100 mg, 0.44 mmol) in DMF (3 mL) was heated to reflux for
0 minutes. The solvent was evaporated in a vacuum, and the residue was
Cl and filtered. The filtrate was washed with concentrated
HCl solution and evaporated. After recrystallization from hexane/CH Cl
dissolved in CH
2
2
2
2
,
8
was obtained as dark violet crystals in 85% yield (25.3 mg, 26.7 mmol).
1
3
H NMR (200 MHz, CDCl
3
): d 9.4 (d, J(H,H) 4.3 Hz, 2H; b-pyrrole),
3
19
9
.0 (d, J(H,H) 4.9 Hz, 2H; b-pyrrole), 8.9 (m, 4H; b-pyrrole); F NMR
3
4
(
188 MHz, CDCl
3
): d � 136.5 (dd, J(F,F) 22.6 Hz, J(F,F) 11.0 Hz,
3 4
2
F; ortho-F), � 136.6 (dd, J(F,F) 22.6 Hz, J(F,F) 9.0 Hz, 1F; ortho-F),
3 4
�
137.9 (dd, J(F,F) 22.6 Hz, J(F,F) 9.0 Hz, 1F; ortho-F), � 138.2 (dd,
4 3
3
J(F,F) 24.9 Hz, J(F,F) 9.0 Hz, 2F; ortho-F), � 152.0 (t, J(F,F)
3
22.6 Hz, 2F; para-F), � 152.2 (t, J(F,F) 22.6 Hz, 1F; para-F), � 161.7
�
4
(
m, 6F; meta-F); UV/Vis (CH
2
Cl
2
): lmax (e  10 ): 396 (4.7), 416 (21.5), 566
[{Fe(tpfc)}
2
O] (5e): (C37
H
8
F
15FeN
4
)
2
O ´ C
7
H
16, M
r
1814.85, orthorhombic,
(
1.5), 588 nm (1.4); MS (DCI ): m/z (%): 949.0 (100) [MH] , 912.9 (20)
space group Pbca, a 13.100(1), b 30.512(1), c 35.631(1) , V
[
MH � Cl] .
Synthesis of [P(tpfc)(OH)
one portion to a boiling solution of 4 (40 mg, 50.2 mmol) in pyridine (4 mL)
under N . After 30 minutes of heating under reflux the solvent was
evaporated, and the residue was dissolved in CH Cl and filtered. The
filtrate was washed with HCl (0.1m), dried, and evaporated. The residue
was passed through a column of silica with CH Cl as eluent, to remove
excess of inorganic salts. After recrystallization from hexane/CH Cl2, 9 was
3
� 3
1
0
4242.0(5) , Z 8, T 110 K,
1
calcd 1.693 gcm
,
m
(MoKa)
2
] (9): POCl
3
(400 mL, 4.3 mmol) was added in
� 1
.54 mm , 12628 unique reflections, R
1
0.068 for 7532 observed reflec-
tions with F
o
> 4s(F
.48 e . One mole of partly disordered n-heptane solvent was included
in the crystal lattice.
Fe(tpfc)(py) ] (5c): C47
o
), R
1
0.134 (wR
2
0.244) for all unique data, jD1 jꢂ
2
� 3
1
2
2
[
2
H
18
F
15FeN
6
´ 1.5(C
5
H
5
N), M
r
1126.17, monoclinic,
2
2
space group C2/c, a 40.725(2), b 8.672(3), c 26.896(1) , b 97.96(1)8,
2
1
3
� 3
V 9407.2(7) , Z 8, T 115 K,
1
calcd 1.590 gcm
,
m
(MoKa)
obtained as red crystals in 87% yield (37.5 mg, 43.7 mmol). H NMR
�
1
3
4
0.43 mm , 8736 unique reflections, R
1
0.101 for 6118 observed reflections
(
400 MHz, [D
6
]benzene): d 8.9 (dd, J(H,H) 4.5 Hz, J(P,H) 2.4 Hz,
3
4
with F
o
> 4s(F
o
), R
0.85 e . The precision of this determination was affected by structural
disorder of some fragments of the structure. Thus, the central C ring
1
0.140 (wR 0.276) for all unique data, jD1 jꢂ
2
2
H; b-pyrrole H), 8.8 (dd, J(H,H) 4.7 Hz, J(P,H) 2.1 Hz, 2H; b-
�
3
3
4
pyrrole H), 8.7 (dd, J(H,H) 4.0 Hz, J(P,H) 2.7 Hz, 2H; b-pyrrole H),
3
4
6 5
F
8
2
2
.6 (dd, J(H,H) 4.4 Hz, J(P,H) 3.3 Hz, 2H; b-pyrrole H), � 5.3 (brs,
19
3
revealed partial orientational disorder, which could not be resolved. The
pyridine molecules contained in the crystal lattice (1.5 molecules per
asymmetric unit) appear severely disordered as well.
22
H; OH); F NMR (188 MHz, [D
6
]benzene): d � 137.60 (dd, J(F,F)
4
3
4.6 Hz, J 8.5 Hz, 6F; ortho-F), � 151.7 (t, J(F,F) 21.2, 1F; para-F),
151.8 (t, 3J(F,F) 21.8, 2F; para-F), � 161.5 (m, 6F; meta-F); UV/Vis
�
�
4
(
CH
2
Cl
2
): lmax (e  10 ): 388 (10.3), 410 (45.3), 560 (5.2), 582 nm (6.6); MS
3 31 15 4 6 6
[Rh{H(N -benz-tpfc)}(CO)(PPh )] (12a): C63H F N OPRh ´ 0.5(C H ),
�
�
�
(
DCI ): m/z (%): 858.1 (20) [M] , 912.9 (100) [M � H
2
O] .
(200 mL, 1.7 mmol) was added in one
portion to a boiling solution of 4 (20 mg, 25.1 mmol) in DMF (3 mL). After
0 minutes of heating under reflux the solvent was evaporated, and the
residue was dissolved in CH Cl and filtered. The filtrate was washed with
M
r
1317.85, monoclinic, space group C2/c, a 34.711(1), b 13.143(1),
3
c 26.951(1) , b 117.81(1)8, V 10874.8(7) , Z 8, T 115 K, 1calcd
Synthesis of [Ge(tpfc)Cl] (7a): GeCl
4
�
3
� 1
1
.610 gcm , m (MoKa) 0.45 mm , 9718 unique reflections, R
1
0.068 for
5
288 observed reflections with F > 4s(F ), R
o
o
1
0.116 (wR 0.169) for all
2
3
�
3
unique data, jD1 jꢂ 1.08 e . One molecule of the benzene solvent was
2
2
located on a twofold rotation axis.
HCl (0.1m), dried and evaporated. After recrystallization from benzene/
heptane, 7a was obtained as dark violet crystals in 90% yield (20.4 mg,
Spectroscopy of metallocorrole cation radicals: Samples for ESR spectro-
scopy were prepared by putting the solid metallocorrole (2 mg, 2.3 mmol)
together with the hexachloroantimonate salt of dibenzo-1,4-dioxin cation
radical (0.5 mg, 1 mmol) in a quartz ESR cuvette and degassing that tube by
1
3
22.6 mmol). H NMR (200 MHz, CDCl
3
): d 9.6 (d, J(H,H) 3.9 Hz, 2H;
3
b-pyrrole H), 9.1 (m, 4H; b-pyrrole H), 8.9 (d, J(H,H) 4.1 Hz, 2H; b-
pyrrole H); 19F NMR (188 MHz, CDCl
): d � 136.4 (d, J(F,F) 25.0 Hz,
3
3
3
3
F; ortho-F) � 137.7 (d, J(F,F) 24.0 Hz, 3F; ortho-F), � 151.80 (t,
vacuum. Dry and degassed CH
2 2
Cl (0.3 mL) was added by vacuum transfer
Chem. Eur. J. 2001, 7, No. 5
ꢀ WILEY-VCH Verlag GmbH, D-69451 Weinheim, 2001 0947-6539/01/0705-1053 $ 17.50+.50/0
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