R.D. Adams et al. / Journal of Organometallic Chemistry 689 (2004) 65–70
69
CH2Cl2 (3:1) solvent mixture. The second and third
bands were collected to give 26.1 mg of green C24S12S2,
2, in 10% yield and 29.7 mg of red C24H14S2, 3, in 11%
yield, respectively.
gram SAINT. An empirical absorption correction based
on the multiple measurement of equivalent reflections
was applied by using the program SADABS. All struc-
tures were solved by a combination of direct methods
and difference Fourier syntheses, and refined by full-
matrix least squares on F 2, by using the SHELXTL
software package [24]. Crystal data, data collection pa-
rameters, and results of the analyses for compounds 1–4
are given in Table 1.
Compounds 1–3 crystallized in the monoclinic crystal
system. For compounds 1 and 2, the space group P21=n
was identified uniquely on the basis of the systematic
absences in the intensity data. Compound 2 contains
two symmetry independent molecules in the asymmetric
crystal unit. Both molecules are structurally similar. For
compound 3 an alternative monoclinic setting P21=c of
the same space group was used. Compound 4 crystal-
lized in the tetragonal crystal system. The space group
P-421c was identified uniquely on the basis of the sys-
tematic absences in the intensity data. All non-hydrogen
atoms were refined with anisotropic displacement pa-
rameters. Hydrogen atoms in compounds 1, 3, and 4
were placed in geometrically idealized positions and in-
cluded as standard riding atoms. Hydrogen atoms in
compound 2 were located and refined with an isotropic
displacement parameter.
4.4. Conversion of 2 to 1
Compound 2 (43.5 mg, 0.120 mmol) was dissolved in
25 mL benzene and irradiated (medium pressure mer-
cury lamp at 360 W). After 30 min, the color of the
reaction mixture changed from green to red. After
cooling, the solvent was removed in vacuo, and the
product was isolated by column chromatography on
silica gel using a hexane/CH2Cl2 (3:1) solvent mixture.
The red band was collected to give 36.1 mg of C24S12S,
1, in 91% yield.
4.5. Synthesis of Pt(COD)(C24H12S2), (4)
Pt(COD)2 (5.0 mg, 0.012 mmol) was added to a so-
lution of 2 (4.5 mg, 0.012 mmol) in 10 mL CH2Cl2. After
30 min, the dark brown mixture was filtered through a
short column of florisil and the solvent was removed by
rotary evaporation. The product was separated by TLC
using a 2:1 hexane/CH2Cl2 mixture. The brown band
was collected to give 1.1 mg of Pt(COD)(C24H12S2), 4, in
14% yield. Spectral data for 4: 1H NMR (CDCl3):
d ¼ 7:87 (d, 2H, Ph), 7.83 (d, 2H, Ph), 7.76 (d, 2H, Ph),
7.74 (d, 2H, Ph), 7.62(t, 2H, Ph), 7.5 (t, 2H, Ph), 5.50–
5.55 (m, 4H, CH, COD), 2.46–2.52 (m, 8H, CH2, COD).
Anal. Found (Calc.): C, 56.90 (57.56); H, 3.08 (3.63)%.
MS (DEP) m/z 668 (Mþ), 332 (Mþ ) Pt(COD)S).
5. Supplementary material
CIF files for the structural analyses have been de-
posited with the Cambridge Crystallographic Data
Centre CCDC 218990–218993 for compounds for 1–4,
respectively.
4.6. Conversion of 4 to 1
Compound 4 (12.2 mg, 0.018 mmol) was dissolved in
benzene and heated to reflux. After 3 h, the mixture was
filtered through a short column of florisil and the solvent
was removed by rotary evaporation. The product was
separated by TLC using a 2:1 hexane/CH2Cl2 mixture.
The red band was collected to give 2.9 mg of 1 in 50%
yield.
Acknowledgements
This research was supported by a grant from the
National Science Foundation, CHE-9909017.
4.7. Crystallographic analysis
References
Red crystals of 1, 2, and 3 and brown crystals of 4
suitable for diffraction analysis were grown by slow
evaporation of solvent from a hexane/methylene chlo-
ride solvent mixture at 5 °C. Each data crystal was glued
onto the end of a thin glass fiber. X-ray intensity
data were measured by using a Bruker SMART APEX
CCD-based diffractometer using Mo Ka radiation
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with the SAINT+ program using a narrow-frame inte-
gration algorithm [23]. Corrections for the Lorentz and
polarization effects were also applied by using the pro-