Palladium(II)–Porphyrin Complex
FULL PAPER
Ag/AgNO3 electrode (0.1m in MeCN); and a platinum wire was the
counter electrode. Tetrabutylammonium hexafluorophosphate (0.1m) was
used as the supporting electrolyte. Before each measurement, the glassy
carbon working electrode was polished with 50 nm alumina, sonicated in
distilled water, and then rinsed with acetone. Electrochemical measure-
ments were conducted at room temperature after degassing the solution
by bubbling with nitrogen.
vent-saturated oxygen was bubbled throughout the whole experiment.
After irradiation, the solvent was evaporated, and the residue was sub-
jected to 1H NMR spectroscopic analysis. Conversions and yields were
calculated by 1H NMR spectroscopic analysis using 4,4’-dimethyl-2,2’-bi-
pyridine as an internal standard.
General procedure for photoinduced oxidative cyanation of tertiary
amines catalyzed by PdF20TPP:
A
mixture of tertiary amine
Gas chromatography: Gas chromatography analyses were performed
using an Agilent 7890A GC system with FID. High-purity helium was
used as the carrier gas, and an Agilent HP-5 column (length=30 m, inter-
nal diameter=0.32 mm, film thickness=0.25 mm) was used.
(0.128 mmol), sodium cyanide (0.256 mmol), acetic acid (0.192 mmol),
and PdF20TPP (0.05 mol%) was dissolved by a mixture of acetonitrile
and methanol (1.6 mL, 1:1 v/v) in a quartz cell. The solution was irradiat-
ed by light (300 W Xe lamp, l>400 nm) for 3 h, and solvent-saturated
oxygen was continuously bubbled throughout the whole experiment.
After that, the solvent was evaporated and the residue was subjected to
1H NMR spectroscopic analysis. Conversions and yields were calculated
by 1H NMR spectroscopic analysis using 4,4’-dimethyl-2,2’-bipyridine as
an internal standard.
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Experimental setup for light-induced oxidative C H functionalization re-
actions: Photoinduced reactions were conducted by irradiating the reac-
tion mixture with a 300 W xenon lamp in a lamp housing (Oriel, model
66485) with an F/1, fused silica aspheric condenser with an arc lamp
power supply (Oriel, model 69911). The output beam was collimated and
the size was 1.3 inches. The output beam first passed through a liquid
filter (Oriel, model 6117) with distilled water inside to absorb infrared ra-
diation. The external chamber of the liquid filter had water circulation to
remove the energy absorbed by the water inside. Optical filters were
placed on a multiple filter holder (Oriel, model 62020), which was
mounted in front of the liquid filter.
General procedure for photoinduced oxidative aza-Henry reaction of ter-
tiary amines catalyzed by PdF20TPP:
A mixture of tertiary amine
(0.128 mmol) and PdF20TPP (0.05 mol%) was dissolved by nitromethane
(1.6 mL) in a quartz cell. The solution was irradiated by light (300 W Xe
lamp, l>400 nm) for 3 h, and solvent-saturated oxygen was continuously
bubbled throughout the whole experiment. After that, the solvent was
evaporated, and the residue was subjected to 1H NMR spectroscopic
analysis. Conversions and yields were calculated by 1H NMR spectro-
scopic analysis using 4,4’-dimethyl-2,2’-bipyridine as an internal standard.
Synthesis of porphyrin complexes: H2Porlac and H2F20Cl8TPP were pre-
pared by literature methods.[10a,20] Platinum(II)– and palladium(II)–por-
phyrin complexes were obtained by heating to reflux the free-base por-
General procedure for photoinduced oxidative coupling reaction of terti-
ary amines with dimethyl malonate catalyzed by PdF20TPP: A mixture of
tertiary amine (0.128mmol), dimethyl malonate (1.28mmol), K2CO3
(0.384mmol), and PdF20TPP (0.05mol%) was dissolved by a mixture of
acetonitrile and methanol (1.6mL, 1:1 v/v) in a quartz cell. The solution
was irradiated by light (300 W Xe lamp, l>400 nm) for 3 h, and solvent-
saturated oxygen was continuously bubbled throughout the whole experi-
ment. After that, the solvent was evaporated, and the residue was sub-
jected to 1H NMR spectroscopic analysis. Conversions and yields were
phyrins with three molar equivalents of [Pt
ACHTUNGTRENNUNG
ACHTUNGRTENN(NUG PhCN)2Cl2] or [Pd-
phere. The progress of the reaction was monitored by UV-visible absorp-
tion spectroscopy. When the reaction was completed, the reaction
mixture was added dropwise to methanol and stored at ꢀ108C for 3 h to
precipitate the product. The crude product was purified by column chro-
matography on SiO2 by using dichloromethane/hexane mixture as eluent.
Data for PtTPP: Yield: 330 mg, 76%; 1H NMR (400 MHz, CDCl3): d=
8.75 (s, 8H), 8.15 (d, J=6.5 Hz, 8H), 7.69–7.78 ppm (m, 12H); MS
(FAB+): m/z: 807.2; elemental analysis calcd (%) for C44H28N4Pt: C
65.42, H 3.49, N 6.94; found: C 65.59, H 3.55, N 6.86.
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calculated by H NMR spectroscopy using 4,4’-dimethyl-2,2’-bipyridine as
an internal standard.
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General procedure for photoinduced oxidative coupling reaction of terti-
ary amines with diethyl phosphite catalyzed by PdF20TPP: A mixture of
tertiary amine (0.128mmol), diethyl phosphite (0.64mmol), and catalyst
(0.05mol%) was dissolved by a mixture of acetonitrile and methanol
(1.6mL, 1:1 v/v) in a quartz cell. The solution was irradiated by light
(300 W Xe lamp, l>400 nm) for 3 h, and solvent-saturated oxygen was
continuously bubbled throughout the whole experiment. After irradia-
tion, the solvent was evaporated, and the residue was subjected to
1H NMR spectroscopic analysis. Conversions and product yields were cal-
Data for PtF20TPP: Yield: 76 mg, 79%; H NMR (400 MHz, CDCl3): d=
8.83 ppm (s, 8H); 19F NMR (376 MHz, CDCl3): d=ꢀ161.0 (m, 8F),
ꢀ151.0 (t, J=22.6 Hz, 4F), ꢀ136.3 ppm (m, 8F); MS (FAB+): m/z:
1167.0; elemental analysis calcd (%) for C44H8F20N4Pt: C 45.26, H 0.69,
N 4.80; found: C 45.12, H 0.74, N 4.82.
Data for PdTPP: Yield: 260 mg, 72%; 1H NMR (400 MHz, CDCl3): d=
8.81 (s, 8H), 8.16 (d, J=6.3 Hz, 8H), 7.71–7.79 ppm (m, 12H); MS
(FAB+): m/z: 720.1; elemental analysis calcd (%) for C44H28N4Pd: C
73.49, H 3.92, N 7.79; found: C 73.32, H 3.88, N 7.71.
Data for PdF20TPP: Yield: 276 mg, 83%; 1H NMR (400 MHz, CDCl3):
d=8.90 ppm (s, 8H); 19F NMR (376 MHz, CDCl3): d=ꢀ161.1 (m, 8F),
ꢀ151.1 (t, J=18.8 Hz, 4F), ꢀ136.4 ppm (m, 8F); MS (FAB+): m/z:
1078.0; elemental analysis calcd (%) for C44H8F20N4Pd: C 48.98, H 0.75,
N 5.19; found: C 49.15, H 0.89, N 5.11.
Data for PdF20Cl8TPP: Yield: 60 mg, 65%; 19F NMR (376 MHz, CDCl3):
d=ꢀ161.39 (t, J=18.8 Hz, 8F), ꢀ148.79 (t, J=22.6 Hz, 4F),
ꢀ137.78 ppm (d, J=15.1 Hz, 8F); MS (FAB+): m/z: 1353.6; elemental
analysis calcd (%) for C44Cl8F20N4Pd: C 39.02, H 0.00, N 4.14; found: C
38.73, H <0.30, N 4.35.
Data for PdPorlac: Yield: 80 mg, 71%; 1H NMR (400 MHz, CDCl3): d=
8.59–8.65 (m, 5H), 8.46 (d, J=4.9 Hz, 1H), 8.03–8.09 (m, 6H), 7.92 (d,
J=6.3 Hz, 2H), 7.65–7.78 ppm (m, 12H); 13C NMR (150 MHz, CDCl3):
d=164.8, 147.7, 145.9, 143.5, 142.0, 140.7, 140.6, 140.1, 139.6, 137.8, 136.8,
133.9, 133.7, 133.5, 132.9, 132.2, 131.0, 130.8, 130.2, 130.0, 129.3, 129.1,
128.3, 128.2, 128.1, 127.7, 127.5, 127.3, 127.0, 123.5, 121.8, 117.6,
103.2 ppm; MS (FAB+): m/z: 736.1; elemental analysis calcd (%) for
C43H26N4O2Pd: C 70.07, H 3.56, N 7.60; found: C 70.24, H 3.65, N 7.61.
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culated by H NMR spectroscopic analysis using 4,4’-dimethyl-2,2’-bipyri-
dine as an internal standard.
General procedure for photoinduced oxidative coupling reaction of terti-
ary amines with acetyl nucleophile catalyzed by PdF20TPP: A mixture of
tertiary amine (0.128mmol), acetyl nucleophile (0.4mL), l-proline
(0.128mmol), and PdII catalyst (0.05mol%) was dissolved by a mixture
of acetonitrile and methanol (1.2mL, 1:2 v/v) in a quartz cell. The solu-
tion was irradiated by light (300 W Xe lamp, l>400 nm) for 3 h, and sol-
vent-saturated oxygen was continuously bubbled throughout the whole
experiment. After irradiation, the solvent was evaporated, and the resi-
due was subjected to 1H NMR spectroscopic analysis. Conversions and
product yields were calculated by using 4,4’-dimethyl-2,2’-bipyridine as
an internal standard.
General procedure for photoinduced oxidative intramolecular coupling
reaction of tertiary amines catalyzed by PdF20TPP: A mixture of tertiary
amine (0.128 mmol), K2CO3 (0.384 mmol), and catalyst (0.05 mol%) was
dissolved by acetonitrile (1.6 mL) in a quartz cell. The solution was irra-
diated by light (300 W Xe lamp, l>400 nm) for 3 h, and solvent-saturat-
ed oxygen was continuously bubbled throughout the whole experiment.
After irradiation, the solvent was evaporated, and the residue was sub-
General procedure for photoinduced oxidation of secondary amines by
porphyrin catalysts: A mixture of secondary amine (0.64 mmol) and cata-
lyst (0.005 mol%) was dissolved by acetonitrile (1.6 mL) in a quartz cell.
The solution was irradiated by light (300 W Xe lamp, l>400 nm). Sol-
1
jected to H NMR spectroscopic analysis. Conversions and product yields
were calculated by 1H NMR spectroscopy using 4,4’-dimethyl-2,2’-bipyri-
dine as an internal standard.
Chem. Eur. J. 2013, 00, 0 – 0
ꢀ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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