Inorganic Chemistry
Article
white solid. Yield: 92% (101 mg). Anal. Calcd for C39H34Au2Cl2P2S2:
C, 42.83; H, 3.13. Found: C, 43.11; H, 3.25. MS (ESI-MS): m/z (%)
1093 (100) [M + 1]+. 1H NMR (CDCl3, ppm) δ 7.52−7.42 (m, 20H),
7.11 (d, J = 9.52 Hz, 2H), 2.75 (t, J = 7.40 Hz, 4H), 2.09−2.01 (m,
2H), 2.03 (s, 6H). 31P NMR (CDCl3, ppm): δ 18.90.
quantum yields were determined by comparing the reaction yields
of the diarylethenes against 1,2-bis(2-methyl-5-phenyl-3-thienyl)per-
fluorocyclopentene.31
Theoretical Methodology. The ground state geometry of 2ooo,
2coc, 2oco, or 2ccc was optimized using Kohn−Sham DFT32 with the
gradient corrected correlation functional level PBE1PBE.33 Based on
the optimized ground state geometries, sixty singlet and six triplet
excited states were obtained to determine the vertical excitation
energies and the oscillator strengths for 2ooo, 2coc, 2oco, or 2ccc
using the time-dependent DFT (TD-DFT) method at the same level
mentioned above.34,35 The conductor-like polarizable continuum
model (PCM)36 with dichloromethane as solvent was used to
calculate in solution. It is a general technique to employ hydrogen
to substitute phenyl in ab initio calculations to save computational
2ooo. Complex Au2(L1o)2Cl2 (54.6 mg, 0.05 mmol) and sodium
methoxide (6.6 mg, 0.12 mmol) were added to a dry THF-MeOH
(20 mL, v/v = 1:1) solution of L2o (51.2 mg, 0.11 mmol) with stirring
at room temperature. The reaction was monitored by TLC. When the
reaction finished, the solvents were removed under reduced pressure.
The residue was then dissolved in 10 mL of CH2Cl2. The solution was
filtered through Celite. Layering n-hexane onto the concentrated
CH2Cl2 solution gave complex 2ooo as a white solid. Yield: 48%
(47 mg). Anal. Calcd for C85H60Au2F12P2S6: C, 52.15; H, 3.09. Found: C,
52.35; H, 3.15. 1H NMR (CDCl3, ppm) δ 7.54−7.47 (m, 16H), 7.43−
7.35 (m, 12H), 7.30−7.28 (m, 2H), 7.24 (s, 2H), 7.19−7.17 (m, 4H),
2.75 (t, J = 7.32 Hz, 4H), 2.07−2.03 (m, 2H), 2.00 (s, 6H), 1.92 (s,
6H), 1.87 (s, 6H). ESI-MS: m/z (%) = 1489 (100) [Au2(L1o)(L2o)]+.
31P NMR (CDCl3, ppm): δ 29.0. IR (KBr): 2106 cm−1 (w, CC).
3oo. A mixture of L2o (117 mg, 0.25 mmol), CuCl (4 mg), and
piperidine (20 mg, 0.25 mmol) was added into toluene (10 mL). The
mixture was heated with stirring at 60 °C for 5 h. The reaction was
monitored by TLC. Upon completion, the solution was concentrated
under reduced pressure. The product was purified by silica gel column
chromatography using dichloromethane-petroleum ether (v/v = 1:4)
as eluent. Yield: 77% (90 mg). ESI-MS: m/z (%) 935 (100) [M + 1]+.
1H NMR (CD2Cl2, ppm): δ 7.54−7.52 (m, 4H), 7.39−7.34 (m, 4H),
7.37 (s, 2H), 7.31−7.27 (m, 2H), 7.24 (s, 2H), 1.95 (s, 6H), 1.94
(s, 6H).
resources. Haberlen and Rosch37 have proved that PH3 provides a
̈
̈
satisfactory model of the full PMe3 or PPh3 for the structural
properties of gold(I) complexes. In these calculations, the Hay−Wadt
double-ξ with a Los Alamos relativistic effect basis set (LANL2DZ)38
consisting of the effective core potentials (ECP) was employed for the
Au atom and 6-31G* basis set was used for the remaining atoms. To
precisely describe the molecular properties, one additional f-type
polarization function was implemented for Au(I) atom (α = 0.2).39 All
the calculations were carried out by using the suite of Gaussian 03
program package.40
ASSOCIATED CONTENT
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S
* Supporting Information
Figures giving additional spectral properties, and tables and
figures of DFT calculations. This material is available free of
1,2-Bis(5-iodo-2-methylthiophen-3-yl)cyclopentene. To an anhy-
drous THF (12 mL) solution of 1,2-bis(5-chloro-2-methylthiophen-3-
yl)cyclopentene (460 mg, 1.40 mmol) was added slowly n-BuLi
(1.6 M in hexane, 1.87 mL, 3 mmol) using a syringe. After the reaction
mixture was stirred for 30 min at room temperature, an anhydrous
THF solution of iodine (2.2 g, 8.64 mmol) was slowly added. The
reaction was monitored by TLC. Upon stirring for 5 h, the reaction
was quenched by an aqueous solution of sodium thiosulfate. The
aqueous layer was separated from the organic layer and extracted with
diethyl ether which was dried with MgSO4. The product was purified
by silica gel column chromatography using petroleum ether as eluent.
AUTHOR INFORMATION
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Corresponding Author
ACKNOWLEDGMENTS
■
We thank financial support from the NSFC (20931006,
U0934003, and 91122006), the 973 project (2007CB815304)
from MSTC, and the NSF of Fujian Province (2011J01065).
1
Yield: 78% (560 mg). ESI-MS: m/z (%) 513 (100) [M + 1]+. H
NMR (CDCl3, ppm): δ 6.89 (s, 2H), 2.73 (t, J = 7.6 Hz, 4H), 2.05−
2.00 (m, 2H), 1.89 (s, 3H), 1.85 (s, 3H).
4ooo. 1,2-Bis(5-iodo-2-methylthiophen-3-yl)cyclopentene (51.2 mg,
0.1 mmol) was dissolved in diisopropylamine (15 mL) at room
temperature. To the solution were added Pd(PPh3)2Cl2 (17 mg, 0.01
mmol) and CuI (2 mg) with stirring for 15 min. Compound L2o
(112 mg, 0.24 mmol) was then added and the reaction mixture was stirred
for another 2 h at room temperature. The reaction was monitored by
TLC. Upon completion, the solution was first filtered and the filtrate
was then concentrated under reduced pressure. The product was
purified by silica gel column chromatography using dichloromethane-
petroleum ether (v/v = 1:2) as eluent. Yield: 70% (83 mg). ESI-MS:
m/z (%) 1193 (100) [M + 1]+. 1H NMR (CD2Cl2, ppm): δ 7.55−7.52
(m, 4H), 7.37 (t, J = 7.5 Hz, 4H), 7.31−7.28 (m, 2H), 7.26 (s, 2H),
7.23 (s, 2H), 6.96 (s, 2H), 2.76 (t, J = 7.46 Hz, 3H), 2.12−2.08 (m,
3H), 1.96 (s, 6H), 1.95 (s, 6H), 1.93 (s, 6H).
REFERENCES
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Physical Measurements. 1H, 19F, and 31P NMR spectra were
performed on a Bruker Avance III (400 MHz) spectrometer with
SiMe4 as the internal reference and H3PO4 as the external reference.
UV−vis absorption spectra were measured on a Perkin-Elmer Lambda
25 UV−vis spectrophotometer. Infrared spectra (IR) were recorded
on a Magna 750 FT-IR spectrophotometer with KBr pellets. Elemental
analyses (C, H, and N) were carried out on a Perkin-Elmer model
240 C elemental analyzer. Electrospray ionization mass spectrometry
(ESI-MS) was recorded on a Finnigan DECAX-30000 LCQ mass
spectrometer using dichloromethane-methanol as mobile phase. ZF5
UV lamp (254 and 365 nm) was used for UV light irradiation, and
visible light irradiation (440, 672, or >460 nm) was carried out by
using a LZG220 V500 W tungsten lamp with cutoff filters. The
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dx.doi.org/10.1021/ic202265u | Inorg. Chem. 2012, 51, 1933−1942