Construction of Gold(III)/Free-Base Porphyrin Dimers
4
4
4
(d, J ) 2 Hz, 2H), 7.94 (d, J ) 2 Hz, 2H), 7.96 (t, J ) 2 Hz,
1H), 8.11-8.23 (m, 8H), 10.23 (s, 2H), 10.63 (s, 2H); HRMS (FAB)
calcd for [C106H120AuN8]+ 1701.9301, found 1701.9332.
(s, 18H), 1.79 (m, 24H), 2.46 (s, 6H), 2.47 (s, 6H), 2.59 (s, 6H),
2.61 (s, 6H), 4.03 (m, 16H), 7.64 (m, 4H), 7.72 (m, 4H), 7.84 (t,
4
4J ) 2 Hz, 1H), 7.88 (d, J ) 2 Hz, 2H), 7.94-8.07 (m, 11H),
H2P-3B-Ethynyl-TIPS. Pd2(dba)3‚CHCl3 (7 mg, 7 µmol) was
added to a deaerated solution of H2P-1B-I (40 mg, 0.046 mmol),
bridge building block TIPS-ethynyl-2B-ethynyl (24 mg, 0.064
mmol), AsPh3 (42 mg, 138 µmol), and NEt3 (640 µL, 4.6 mmol)
in CH2Cl2/methanol (1:1, 14 mL). The reaction mixture was stirred
for 1 h at 40 °C, and the solvent was removed in vacuo. A short
plug of silica gel (CH2Cl2 followed by 2% MeOH in CH2Cl2) and
SEC (toluene) gave H2P-3B-ethynyl-TIPS as a red solid (47
mg, 0.042 mmol, 92%): 1H NMR (CDCl3) δ -2.40 (br s, 2H),
1.15 (m, 21H), 1.51 (s,18H), 1.78 (m, 12H), 2.47 (s, 6H), 2.55 (s,
6H), 4.03 (m, 8H), 7.50 (m, 4H), 7.60 (d, 3J ) 8 Hz, 2H), 7.68 (d,
10.11 (s, 2H), 10.55 (s, 2H); HRMS (FAB) calcd for [C122H126
-
AuN8Zn]+ 1963.9062, found 1963.9072.
[ZnP-5B-AuP]+BF4- was prepared from [H2P-5B-AuP]+-
-
BF4 (16 mg, 0.0077 mmol), as described for [ZnP-2B-
AuP]+BF4-, and gave [ZnP-5B-AuP]+BF4 as a red solid (15
-
mg, 0.0067 mmol, 90%): 1H NMR (CDCl3) δ 1.53 (s, 18H), 1.54
(s, 18H), 1.78 (m, 24H), 2.45 (s, 6H), 2.46 (s, 6H), 2.59 (s, 6H),
2.60 (s, 6H), 4.02 (m, 16H), 7.56 (s, 4H), 7.61 (d, 3J ) 8 Hz, 4H),
3
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7.71 (d, J ) 8 Hz, 4H), 7.84 (t, J ) 2 Hz, 1H), 7.88 (d, J ) 2
Hz, 2H), 7.92-8.06 (m, 11H), 10.09 (s, 2H), 10.54 (s, 2H); HRMS
(FAB) calcd for [C130H130AuN8Zn]+ 2063.9375, found 2063.9361.
H2P-nB from ZnP-nB: General Procedure. The corre-
sponding zinc porphyrin, ZnP-nB (∼10 µmol), was dissolved in
dichloromethane and washed twice with 1 M aqueous HCl, twice
with aqueous NaHCO3 (10% w/w), and twice with water. The
solvent was evaporated to give near quantitative yields of H2P-
nB. The highly insoluble products were transferred as a suspension
to the reaction vessel for gold insertion without further characteriza-
tion.
3J ) 8 Hz, 2H), 7.81 (t, J ) 2 Hz, 1H), 7.92 (d, J ) 2 Hz, 2H),
4
4
3
3
7.94 (d, J ) 8 Hz, 2H), 8.11 (d, J ) 8 Hz, 2H), 10.24 (s, 2H);
HRMS (FAB) calcd for [C79H90N4Si]+ 1122.6935, found 1122.6937.
H2P-3B-Ethynyl. A sample of H2P-3B-ethynyl-TIPS (23
mg, 0.020 mmol) was dissolved in THF (3 mL). Bu4NF (25 µmol,
25 µL of a 1.0 M solution in THF) was added, and the mixture
was stirred at room temperature for 30 min, during which time the
color turned darker red. Methanol was added to precipitate the
porphyrin, and subsequent centrifugation gave H2P-3B-ethynyl
as a red solid (17 mg, 0.018 mmol): 1H NMR (CDCl3) δ -2.44
(br s, 1H), -2.42 (br s, 1H), 1.51 (s, 18H), 1.78 (m, 12H), 2.46 (s,
6H), 2.56 (s, 6H), 3.20 (s, 1H), 4.03 (m, 8H), 7.52 (m, 4H), 7.61
[AuP-2B]+BF4-. A solution of H2P-2B (10 mg, 0.012 mmol),
[Au(tht)2]+BF4- (0.054 mmol, 5.4 mL from a 10 mM stock solution
in chlorobenzene), and 2,6-lutidine (0.036 mmol, 720 µL from a
50 mM stock solution in chlorobenzene) in chlorobenzene and
chloroform (1:1, 5 mL) was stirred under argon at 40 °C overnight.
After the solvent was evaporated, the residue was dissolved in CH2-
Cl2 and added to a chromatographic column (Al2O3, neutral, grade
III). Residues of the free-base porphyrin were removed by elution
with pure CH2Cl2. The gold porphyrin was collected by elution
with 3% MeOH in CH2Cl2. The resulting CH2Cl2 solution was
washed twice with dilute aqueous KBF4 and twice with H2O to
ensure the integrity of the anion. Precipitation of the gold porphyrin
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(d, J ) 8 Hz, 2H), 7.70 (d, J ) 8 Hz, 2H), 7.81 (t, J ) 2 Hz,
1H), 7.92 (d, 3J ) 2 Hz, 2H), 7.94 (d, 3J ) 8 Hz, 2H), 8.11 (d, 3J
) 8 Hz, 2H), 10.24 (s, 2H); HRMS (FAB) calcd for [C70H70N4]+
966.5600, found: 966.5618.
[H2P-4B-AuP]+BF4- was prepared from [AuP-1B-I]+BF4
-
(15 mg, 0.013 mmol) and H2P-3B-ethynyl (15 mg, 0.016 mmol),
as described for [H2P-2B-AuP]+BF4-, and gave [H2P-4B-
-
AuP]+BF4 as a red solid (22 mg, 0.011 mmol, 85%): 1H NMR
-
from CH2Cl2 by addition of pentane gave [AuP-2B]+BF4 as a
(CDCl3) δ -2.38 (br s, 2H), 1.52 (s, 18H), 1.53 (s, 18H), 1.79 (m,
12H), 1.84 (m, 12H), 2.47 (s, 6H), 2.55 (s, 6H), 2.58 (s, 6H), 2.67
(s, 6H), 4.02 (m, 8H), 4.13 (m, 8H), 7.65 (m, 4H), 7.73 (m, 4H),
red solid (13 mg, 0.0115 mmol, 96%): 1H NMR (CDCl3) δ 1.52
(s, 18H), 1.84 (m, 12H), 2.57 (s, 6H), 2.68 (s, 6H), 4.13 (m, 8H),
4
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4
7.82 (t, J ) 2 Hz, 1H), 7.87 (d, J ) 2 Hz, 2H), 7.92 (d, J ) 2
Hz, 2H), 7.96 (m, 3H), 8.08 (m, 6H), 10.23 (s, 2H), 10.63 (s, 2H);
HRMS (FAB) calcd for [C122H128AuN8]+ 1901.9927, found
1901.9935.
7.46 (m, 3H), 7.72 (m, 2H), 7.85 (d, J ) 2 Hz), 7.94 (t, J ) 2
Hz, 1H), 8.06 (m, 4H), 10.65 (s, 2H); HRMS (FAB) calcd for
[C60H64AuN4]+ 1037.4796, found 1037.4791.
[AuP-4B]+BF4 was prepared from H2P-4B (16 mg, 0.014
-
[H2P-5B-AuP]+BF4- was prepared from [AuP-1B-I]+BF4
-
mmol), as described for [AuP-2B]+BF4-, and gave [AuP-
-
4B]+BF4 as a red solid (12 mg, 0.009 mmol, 64%): 1H NMR
(18 mg, 0.016 mmol) and H2P-4B-ethynyl (20 mg, 0.019 mmol),
as described for [H2P-2B-AuP]+BF4-, and gave [H2P-5B-
(CDCl3) δ 1.53 (s, 18H), 1.84 (m, 12H), 2.57 (s, 6H), 2.68 (s, 6H),
-
AuP]+BF4 as a red solid (27 mg, 0.013 mmol, 82%): 1H NMR
3
4.13 (m, 8H), 7.36 (m, 3H), 7.53 (m, 6H), 7.59 (d, J ) 8 Hz),
3
4
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(CDCl3) δ -2.45 (br s, 2H), 1.51 (s, 18H), 1.53 (s, 18H), 1.78 (m,
12H), 1.84 (m, 12H), 2.47 (s, 6H), 2.55 (s, 6H), 2.58 (s, 6H), 2.67
(s, 6H), 4.02 (m, 8H), 4.13 (m, 8H), 7.58 (s, 4H), 7.63 (m, 4H),
7.69 (d, J ) 8 Hz, 2H), 7.85 (d, J ) 2 Hz, 2H), 7.95 (t, J ) 2
Hz, 1H), 8.07 (m, 4H), 10.65 (s, 2H); HRMS (FAB) calcd for
[C76H72AuN4]+ 1237.5422, found 1237.5419.
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[AuP-5B]+BF4 was prepared from H2P-5B (6 mg, 0.0053
7.71 (m, 4H), 7.82 (t, J ) 2 Hz, 1H), 7.87 (d, J ) 2 Hz, 2H),
4
mmol), as described for [AuP-2B]+BF4-, and gave [AuP-
7.92 (d, J ) 2 Hz, 2H), 7.95 (m, 3H), 8.07 (m, 6H), 10.22 (s,
2H), 10.63 (s, 2H); HRMS (FAB) calcd for [C130H132AuN8]+
2002.0240, found 2002.0251.
5B]+BF4 as a red solid (6.8 mg, 0.0048 mmol, 91%); H NMR
(CDCl3) δ 1.53 (s, 18H), 1.84 (m, 12H), 2.58 (s, 6H), 2.68 (s, 6H),
-
1
[ZnP-2B-AuP]+BF4-. [H2P-2B-AuP]+BF4- (21.5 mg, 0.012
mmol) was dissolved in 10 mL of CHCl3, and Zn(OAc)2‚2H2O
(26 mg, 0.120 mmol) dissolved in MeOH (1 mL) was added. The
reaction was stirred at room temperature for 3 h. The reaction
mixture was washed twice with 10% NaHCO3, twice with dilute
aqueous KBF4, and twice with water. Evaporation of the solvent
gave [ZnP-2B-AuP]+BF4- as a red solid (22.3 mg, 0.012 mmol,
100%): 1H NMR (CDCl3) δ 1.54 (s, 18H), 1.55 (s, 18H), 1.79 (m,
12H), 1.86 (m, 12H), 2.48 (s, 6H), 2.55 (s, 6H), 2.60 (s, 6H), 2.71
(s, 6H), 4.01 (m, 8H), 4.12 (m, 8H), 7.85 (t, 4J ) 2 Hz, 1H), 7.89
3
4.13 (m, 8H), 7.37 (m, 3H), 7.54 (m, 12H), 7.62 (d, J ) 8 Hz,
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2H), 7.70 (d, J ) 8 Hz, 2H), 7.86 (d, J ) 2 Hz, 2H), 7.95 (t, J
) 2 Hz, 1H), 8.07 (m, 4H), 10.65 (s, 2H); HRMS (FAB) calcd for
[C84H76AuN4]+ 1337.5735, found 1337.5747.
Acknowledgment. This work was supported by grants from
the Swedish Research Council.
Supporting Information Available: General experimental
methods. General procedure and product yield determination for
the reaction carousel experiments. General procedure and product
yield determination for the coupling study of different arylic iodides.
Proton decoupled 13C NMR spectra and positive FAB HRMS
spectra. This material is available free of charge via the Internet at
4
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(d, J ) 2 Hz, 2H), 7.97 (m, 3H), 8.12 (m, 6H), 8.22 (d, J ) 8
Hz, 2H), 10.16 (s, 2H), 10.60 (s, 2H); HRMS (FAB) calcd for
[C106H118AuN8Zn]+ 1763.8436, found 1763.8435.
[ZnP-4B-AuP]+BF4- was prepared from [H2P-4B-AuP]+-
-
BF4 (16 mg, 0.008 mmol), as described for [ZnP-2B-
AuP]+BF4-, and gave [ZnP-4B-AuP]+BF4 as a red solid (13
-
mg, 0.0063 mmol, 79%): 1H NMR (CDCl3): δ 1.53 (s, 18H), 1.54
JO052423V
J. Org. Chem, Vol. 71, No. 4, 2006 1687