filtered to remove the very fine powder of mercury and the
filtrate was evaporated in vacuo. The residue was finally redis-
solved in CH2Cl2 (ca. 2 cm3) and separated by preparative TLC
using n-hexane–CH2Cl2 (7:3 v/v) as the eluent to afford two
bands with Rf ca. 0.7 and 0.55, which were extracted from silica
to yield yellow complex 1 (352 mg, 0.134 mmol, 25%) and
orange complex 2 (341 mg, 0.161 mmol, 30%) respectively
(Found: C, 15.41; H, 0.30; N, 1.09. Calc. for C34H8Hg2N2O24-
Os7S2 1: C, 15.42; H, 0.30; N, 1.07%. Found: C, 16.98; H, 0.37;
N, 1.30. Calc. for C30H8HgN2O20Os6S2 2: C, 16.96; H, 0.38;
N, 1.32%).
H, 0.60; N, 3.28. Calc. for C56H20HgN8O28Os10S2 7: C, 19.65;
H, 0.58; N, 3.28%).
Reaction of [Ru (CO) ] with [PhHgSC(N᎐NPh)(᎐NNHPh)]
᎐
᎐
3
12
[Ru (CO) ] (639 mg, 1.0 mmol) and [PhHgSC(N᎐NPh)-
᎐
3
12
(᎐NNHPh)] (530 mg, 1.0 mmol) were dissolved in 50 cm3 of
᎐
CHCl3 and the dark red solution allowed to reflux for 3 h. The
reaction mixture was then filtered to remove the very fine
powder of mercury and excess solvent was removed under
reduced pressure, yielding a deep brown residue. This residue
was then dissolved in a minimum amount of CH2Cl2 and
subject to preparative TLC on silica using n-hexane–CH2Cl2
(1:1 v/v) as eluent. Other than the traces of [Ru3(CO)12], two
orange and one red bands with Rf ca. 0.85, 0.7 and 0.5,
respectively were obtained and characterized as 8 (118 mg,
0.15 mmol, 15%), 9 (122 mg, 0.15 mmol, 15%) and 10 (442
mg, 0.456 mmol, 45%), respectively (Found: C, 46.01; H,
2.69; N, 7.17. Calc. for C30H21N4O5Ru2S2 8: C, 45.98; H, 2.68;
N, 7.15. Found: C, 45.80; H, 2.60; N, 6.90. Calc. for C31H23-
N4O7Ru2S2 9: C, 45.82; H, 2.59; N, 6.90. Found: C, 51.38; H,
3.45; N, 11.43. Calc. for C42H34N8O4Ru2S2 10: C, 51.37; H,
3.47; N, 11.41%).
Reaction of [Ru3(CO)10(NCMe)2] with [PhHgS(C5H4N)]
To a CH2Cl2 solution of freshly prepared [Ru3(CO)10(NCMe)2]
(85 mg, 0.128 mmol), [PhHgS(C5H4N)] (49 mg, 0.128 mmol)
was added at room temperature. The reaction mixture gradually
changed from pale yellow to red upon addition. Reactions
were completed after stirring for 1 h, as monitored by TLC
and IR. The reaction solution was concentrated in vacuo and
the residue redissolved in CH2Cl2 (ca. 2 cm3) and separated
by TLC using n-hexane–CH2Cl2 (1:1 v/v). This afforded
[Ru3(CO)12] and a red complex 3 (119.51 mg, 0.061 mmol,
48%) with Rf ca. 0.5 as the sole product (Found: C, 19.69;
H, 0.42; N, 1.47. Calc. for C32H8Hg2N2O22Ru7S2 2: C, 19.74;
H, 0.41; N, 1.44%).
Carbonylation of complex 8 in CH2Cl2
Complex 8 (20 mg, 0.025 mmol) was dissolved in CH2Cl2 (30
ml) and the orange solution stirred at room temperature for 6 h.
The solvent was removed under reduced pressure and the only
product isolated by TLC, using n-hexane–CH2Cl2 (1:1, v/v) as
the eluent, was 9 (Rf = 0.85, 15 mg, 0.02 mmol, 75%) accom-
panied by a small amount of unreacted 8 (Rf = 0.7, 3 mg, 0.003
mmol, 15%).
Reaction of [Os3(CO)10(NCMe)2] with [PhHgS(mbt)]
(Hmbt ؍
2-mercaptobenzothiazole)
A yellow solution of [Os3(CO)10(NCMe)2] (500 mg, 0.536
mmol) in CH2Cl2 was stirred with 1 equivalent of [PhHg(mbt)]
(239 mg, 0.54 mmol) under N2. The colour gradually turned
orange–red and powdery mercury was deposited. Stirring was
continued until all starting materials were consumed (TLC
monitoring, ca. 1.5 h). The reaction mixture was then filtered to
remove the very fine powder of mercury and the filtrate was
evaporated in vacuo. The residue was finally redissolved in
CH2Cl2 (ca. 2 cm3) and separated by preparative TLC using
n-hexane–CH2Cl2 (3:2 v/v) as the eluent to afford two bands
with Rf ca. 0.8 and 0.65, which were extracted from silica to
yield orange complex 4 (419 mg, 0.188 mmol, 35%) and yel-
low complex 5 (149 mg, 0.107 mmol, 20%), respectively
(Found: C, 18.29; H, 0.40; N, 1.25. Calc. for C34H8HgN2O20-
Os6S4 4: C, 18.26; H, 0.36; N, 1.25. Found: C, 20.75; H, 0.89; N,
2.04. Calc. for C24H12HgN2O10Os3S4 5: C, 20.75; H, 0.86; N,
2.02%).
Thermolysis of complex 9
Complex 9 (20 mg, 0.025 mmol) was dissolved in n-hexane (30
ml). The orange solution was refluxed under a dinitrogen
atmosphere. Using IR spectroscopic monitoring, no visible
change was observed after 4 h.
Crystallography
All pertinent crystallographic data and other experimental
details are summarized in Table 12. Intensity data were col-
lected at ambient temperature on either a Rigaku AFC7R dif-
fractometer (complexes 1, 2 and 3) or a MAR research image
plate scanner (complexes 4–10) equipped with graphite-crystal
monochromated Mo-Kα radiation (λ = 0.71073 Å) using ω–2θ
and ω scan types, respectively. The diffracted intensities were
corrected for Lorentz and polarization effects. Absorption cor-
rection by φ-scan techniques was done for 1, 2 and 3. However,
for complexes 4–10, an approximate absorption correction by
interimage scaling was also applied. Scattering factors were
taken from ref. 29(a) and anomalous dispersion effects29b were
included in Fc. The structures were solved by direct methods
(SIR8830 for 10; SIR9231 for 4, 5; SHELX8632 for 1–3 and 6–9)
and expanded by Fourier-difference techniques (DIRDIF94).33
The solutions were refined by full-matrix least-squares anal-
ysis on F. For all structures, the heavy atoms Hg, Os and S
were refined anisotropically. Attempts to refine all the atoms
anisotropically were made, however, in structures 1–4 and 7,
but led negative anisotropic displacement parameters. There-
fore some non-hydrogen atoms were refined isotropically.
Hydrogen atoms were generated in their ideal positions,
except N(H) which were located from a difference Fourier
synthesis and included in the structure factor calculations
but not refined. Calculations were performed on a Silicon-
Thermolysis of cluster 5
Cluster 5 (100 mg, 0.072 mmol) was refluxed in CHCl3 under an
inert atmosphere. The reaction was monitored by TLC and IR
and completed after about 6 h. The solvent was then removed in
vacuo and redissolved in CH2Cl2 (3 cm3). TLC purification
(eluent: n-hexane–CH2Cl2 (1:1 v/v)) afforded 4 (58 mg, 0.026
mmol, 36%) and unreacted starting material 5 (5 mg, 0.004
mmol, 5%).
Reaction of [Os C(CO) ] with [PhHgSC(N᎐NPh)(᎐NNHPh)]
᎐
᎐
5
15
[Os C(CO) ] (500 mg, 0.361 mmol) and [PhHgSC(N᎐NPh)-
᎐
5
15
(᎐NNHPh)] (191 mg, 0.361 mmol) were stirred at reflux in
᎐
CHCl3 (150 ml) for 12 h after all starting materials had been
consumed. The colour gradually turned from yellow to red-
dish brown. After reduction in volume, the filtrate was separ-
ated by preparative TLC on silica with an eluent of
n-hexane–CH2Cl2 (3:2 v/v) to give two bands which were
extracted from silica to yield red complex 6 (Rf ca. 0.85, 294
mg, 0.094 mmol, 26%) and purple complex 7 (Rf ca. 0.55, 420
mg, 0.123 mmol, 34%) (Found: C, 16.14; H, 0.33. Calc. for
C42H10HgO28Os10S2 6: C, 16.11; H, 0.32. Found: C, 19.67;
Graphics
computer,
using
the
program
package
TEXSAN.34
CCDC reference number 186/1521.
graphic files in .cif format.
2508
J. Chem. Soc., Dalton Trans., 1999, 2497–2510
Kong, Fung-Sze
