Inorganic Chemistry
ARTICLE
were evaluated using the fourth-order MøllerꢀPlesset perturbation theory
[MP4(SDQ)] in combination with PBE0 parametrization.
’ ASSOCIATED CONTENT
S
Supporting Information. This material is available free
b
Synthesis of the Compounds. Tris(bis(trimethylsilyl)amido)-
bismuth Bi{N(SiMe3)2}3 (1). Synthesis in accordance to refs 22 and 23:
2.05 g (19.5 mmol) of BiCl3 dissolved in 20 mL of THF were added
dropwise to a solution of 3.27 g (6.5 mmol) of LiN(SiMe3)2 in 10 mL of
THF at 10 °C under inert atmosphere. The solution was stirred for 3 h,
during which the solution turned shimmering orange, followed by
evaporation of the solvent. Subsequently, the residue was dissolved in
pentane, filtered, and evaporated to dryness, yielding the pale yellow
solid product. Analytical data are consistent with literature values22
(2.31 g (3.34 mmol); 51.5% yield).
’ AUTHOR INFORMATION
Corresponding Author
*Phone:þ43-732-2468-8811 (W.S.); þ43-732-2468-8800 (G.K.).
E-mail: wolfgang.schoefberger@jku.at (W.S.); guenther.knoer@
jku.at (G.K.).
Tris-Pentafluorophenylcorrole H3(TpFPC) (2). Synthesis in accor-
dance to ref 18: 1.52 g (8 mmol) of pentafluorobenzaldehyde was mixed
with 80 μL of a 10% TFA in CH2Cl2 and 840 μL (12 mmol) of pyrrole at
40 °C and vigorously stirred. After 10 min, 80 mL of CH2Cl2 and 2.2 g
(9.6 mmol) of DDQ in 16 mL of THF/toluene 1:1 were added and
stirred for further 5 min. Subsequently, the solution was passed over a
chromatography column (silica; hexane:dichloromethane 2:1) and
further purified by column chromatography using the same solvents
(230 mg (0.288 mmol); 10.8% yield). Crystals suitable for single-crystal
structure determination were obtained by slow evaporation of CHCl3.
Complementary data: 1H NMR (500 MHz, CDCl3, 25 °C): δ = 9.10
(d, J = 4.1 Hz, 2H, H2 þ H18), 8.76 (d, J = 4.5 Hz, 2H, H7 þ H13),
8.55ꢀ8.60 (4H, 2d overlapping, H8 þ H12 and H3 þ H17). 19F NMR
(564.7 MHz, CDCl3, 30 °C): ꢀ137.2 (2F), ꢀ137.7 (4F), ꢀ152.2 (2F),
ꢀ152.7 (1F), ꢀ161.4 (4F), ꢀ161.9 (2F). MS (ESIꢀ): m/z calcd for
C37H10F15N4, 795.07; found, 795.20 [M ꢀ H]ꢀ. UVꢀvis (THF):
λmax = 408, 418(sh), 563, 604 nm.
Bismuth tris-Pentafluorophenylcorrole Bi(TpFPC) (3). Under N2
atmosphere, 50 mg (0.063 mmol) of H3(TpFPC) (2) was dissolved
in 15 mL of abs. THF and 55 mg (0.078 mmol) of Bi{N(SiMe3)2}3 dis-
solved in 2 mL of THF were added dropwise under permanent stirring.
After 12 h at room temperature, during which the color of the reaction
mixture changed from dark violet to dark green and the intense red fluo-
rescence of the free-base corrole completely vanished (the reaction pro-
gress was followed with UVꢀvis spectroscopy), the solvent was
evaporated and the crude product was purified with column chroma-
tography (silica, hexane:dichloromethane 2:1) (45 mg (0.045 mmol);
71.3% yield).
’ ACKNOWLEDGMENT
Financial support of this work by the Austrian Science Fund
(FWF project P18384 “Solid state and Liquid NMR of biomo-
lecular Metalcomplexes” and FWF project P21045 “Bio-inspired
Multielectron Transfer Photosensitizers”) is gratefully acknowledged.
We wish to thank Dr. Roland Fischer for valuable discussion and
measurement of the 19F NMR spectra.
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1H NMR (500 MHz, THF-d8, 25 °C): δ = 9.12 (d, J = 4.1 Hz, 2H,
H2 þ H18), 8.91 (d, J = 4.0 Hz, 2H, H7 þ H13), 8.63 (d, J = 4.1 Hz, 2H,
H8 þ H12), 8.49 (d, J = 4.0 Hz, 2H, H3 þ H17). 19F NMR (282.4 MHz,
THF-d8, 30 °C) δ = ꢀ138.9 (dd, 3J = 24.3 Hz, 4J = 8 Hz, 1F, Fo), ꢀ139.3
(dd, 3J = 24.4 Hz, 4J = 8.2 Hz, 2F, Fo), ꢀ139.6 (dd, 3J = 24.9 Hz, 4J = 8.2
Hz, 2F, Fo), ꢀ140.0 (dd, 3J = 24.9 Hz, 4J = 8 Hz, 1F, Fo), ꢀ157.3 (t, 3J =
20.6 Hz, 2F, Fp), ꢀ157.6 (t, 3J = 20.8 Hz, 1F, Fp), ꢀ164.9 (ddd, 3J =
21.0 Hz, 4J = 7.9 Hz, 2F, Fm), ꢀ165.2 (ddd, 3J = 21.0 Hz, 4J = 8.1 Hz, 1F,
Fm), ꢀ165.6 (m, 3F, Fm). 13C NMR (125.8 MHz, CDCl3, 25 °C): δ =
116.8 (CH, 2C, C2 þ C18), 126.3 (CH, 2C, C7 þ C13), 122.5 (CH, 2C,
C8 þ C12), 121.5 (CH, 2C, C3 þ C17). MS (MALDI): m/z calcd for
C37H8BiF15N4, 1002.031; found (Mþ), 1002.198. UVꢀvis (THF):
λmax(ε) = 322 (21 300), 446 (112 300), 552 (5100), 591 (9200), 631
(14 200).
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and 1 mg (1 μmol) of 3 dissolved in 20 mL of ethanol under O2
atmosphere were heated (60 °C) and simultaneously irradiated for 6
h with the light from a 150 W high-pressure mercury lamp (Heraeus
Noblelight) filtered by a Schott GG 455 nm cutoff filter.
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dx.doi.org/10.1021/ic200840m |Inorg. Chem. 2011, 50, 6788–6797