1078
K.M. Hanif et al. / Polyhedron 19 (2000) 1073–1080
the formation of bidentate chelate as well as monodentate
thiolate bridge.
CH2Cl2 at y208C. Analytical and spectral data for 3: IR
(n(CO), hexane): 2086s, 2055vs, 2018vs, 2004s, 1994s,
1
1966w cmy1. H NMR (CDCl3): d 2.19 (s, 4H), 1.89 (s,
2H). MS (m/z): 478, Mq, 450 [MyCO]q, 422
[My2CO]q, 394 [My3CO]q, 366 [My4CO]q, 338
[My5CO]q, 310 [My6CO]q. Anal. Calc. for C9H6O6-
Ru2S2: C, 22.69; H,1.27. Found: C, 22.78; H, 1.43%.
3. Experimental
All the reactions were routinely carried out under a pre-
purified nitrogen atmosphere. Reagent grade solvents were
freshly distilled from appropriate drying agents. Infrared
spectra were recorded on a Schimadzu FTIR 8101 spectro-
photometer. NMR spectra were recorded on a Varian Unity
Plus 400 spectrometer. [Ru3(CO)12] was purchased from
Strem Chemicals Inc. and used without further purification.
[Os3(CO)10(MeCN)2] was prepared according to the
known procedure [40].
3.3. Thermolysis of 2
A THF solution (30 ml) of 2 (0.120 g, 0.094 mmol) was
refluxed for 1.5 h. The solvent was removed under reduced
pressure and the residue was chromatographed by TLC on
silica gel. Elution with hexane/CH2Cl2 (9:1, v/v) afforded
3 (0.012 g, 34%) as pale yellow crystals.
3.1. Reaction of [Ru3(CO)12] with 1,2-ethanedithiol
3.4. Reaction of [Os3(CO)10(MeCN)2] with 1,2-ethane-
dithiol
A THF solution (80 ml) of [Ru2(CO)12] (0.200g, 0.312
mmol) and 1,2-ethanedithiol (0.059 g, 0.626 mmol) was
refluxed for 1 h. The solvent was removed under reduced
pressure and the residue chromatographed by TLC on silica
gel. Elution with hexane/CH2Cl2 (9:1, v/v) gave two
bands. The major band afforded the known compound
[Ru2(CO)6(m-SCH2CH2S)] (0.050 g, 40%) as pale yellow
crystals after recrystallization from hexane/CH2Cl2 at
y208C. IR (n(CO), hexane): 2085m, 2056vs, 2018vs,
2004s, 1995m, 1968w cmy1. 1H NMR (CDCl3): d 2.37 (s).
13C {1H} NMR (CDCl3): carbonyl region, 196.2 (4C),
188.6 (2C), hydrocarbon region, 36.1 (2C). MS (m/z): 464,
Mq, 436 [MyCO]q, 408 [My2CO]q, 380 [My3CO]q,
352 [My4CO]q, 324 [My5CO]q, 296 [My6CO]q.
Anal. Calc. for C8H4O6Ru2S2: C, 20.78; H, 0.87. Found: C,
20.95; H, 0.95%.
To a dichloromethane solution (15 ml) of [Os3(CO)10-
(MeCN)2] (0.194 g, 0.208 mmol) was added 1,2-ethane-
dithiol (0.039 g, 0.414 mmol) and the reaction mixture was
stirred at room temperature for 5 h. The solvent was removed
by rotary evaporation and the residue was chromatographed
by TLC on silica gel. Elution with hexane/CH2Cl2 (4:1,
v/v) gave two bands. The faster moving major band gave
[(m-H)Os3(CO)10(m-SCH2CH2SH)] (4) as yellow crys-
tals (0.117 g, 60%) from hexane/CH2Cl2 at 208C and the
second band gave too small an amount of a compound for
complete characterization. Spectral and analytical data for 4:
IR (n(CO) hexane): 2110m, 2069vs, 2060s, 2026vs, 2021m,
2001s, 1992m, 1986w cmy1. 1H NMR (CDCl3): d 2.70 (q,
2H, Js8.4 Hz), 2.55 (t, 2H, Js8.4 Hz), 1.65 (t, 1H, Js8.4
Hz), y17.41 (s, 1H). Anal. Calc. for C12H6O10Os3S2:
C, 15.25; H, 0.64. Found: C, 15.42; H, 0.78%. MS (m/z):
950 (Mq), 922 [MyCO]q, 894 [My2CO]q, 866
[My3CO]q 838 [My4CO]q, 810 [My5CO]q, 782
[My6CO]q,, 754 [My7CO]q, 726 [My8CO]q, 698
[My9CO]q, 670 [My10CO]q.
3.2. Reaction of [Ru3(CO)12] with 1,3-propanedithiol
To a THF solution (100 ml) of [Ru3(CO)12] (0.400 g,
0.625 mmol) was added 1,3-propanedithiol (0.135 g, 1.25
mmol) and the reaction mixture was refluxed for 1 h. The
solvent and excess thiol were removed in vacuo and the
residue was chromatographed by TLC on silica gel. Elution
with hexane/CH2Cl2 (9:1, v/v) developed two bands. The
faster moving band afforded [{(m-H)Ru3(CO)10}2(m-
SCH2CH2CH2S)] (2) (0.120 g, 30%) as orange crystals
after recrystallization from hexane/CH2Cl2 at y208C. Ana-
lytical and spectral data for 2: (IR n(CO), hexane): 2105m,
3.5. Reaction of [Os3(CO)10(MeCN)2] with 1,3-propane-
dithiol
1,3-Propanedithiol (0.046 g, 0.428 mmol) was added to
a dichloromethane solution (15 ml) of [Os3(CO)10-
(MeCN)2] (0.200 g, 0.214 mmol) in CH2Cl2 (15 ml) and
the reaction mixture was stirred at room temperature for 3 h.
The solvent was removed under reduced pressure and the
residue was chromatographed by TCL on silica gel. Elution
with hexane/CH2Cl2 (4:1, v/v) gave one major band which
afforded [{m-H)Os3(CO)10}2(m-SCH2CH2CH2S)] (5)
(0.056 g, 30%) as yellow crystals from hexane/CH2Cl2 at
y208C. Analytical and spectral data for 5: IR (n(CO),
hexane): 2110w, 2070s, 2060m, 2027s, 2022m, 2000m,
1991m cmy1. 1H NMR (CDCl3): d 2.44 (t, 4H, Js7.4 Hz),
1.91 (q, 2H, Js7.4 Hz), y17.42 (s, 2H). Anal. Calc. for
1
2067vs, 2057s, 2027vs, 2010w, 1998w cmy1. H NMR
(CDCl3): d 2.25 (t, 4H, Js7.6 Hz), 2.05 (q, 2H, Js7.6
Hz), y15.41 (s, 2H). 13C{1H} NMR (CDCl3): carbonyl
region, d 204.1 (2C), 202.6 (2C), 198.1 (4C), 192.8 (4C),
191.5 (4C), 184.5 (4C), hydrocarbon region, d 55.1 (2C),
35.7 (1C). Anal. Calc. for C23H8O20Ru6S2: C, 21.67; H, 0.63.
Found: C, 21.82; H, 0.75%. The second band gave
[Ru2(CO)6(m-SCH2CH2CH2S)] (3) (0.056 g, 19%) as
pale yellow crystals after recrystallization from hexane/
Tuesday May 23 10:51 AM
StyleTag -- Journal: POLY (Polyhedron) Article: 3427
Hanif, Khandakar M
