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Diphenyl disulfide was prepared by oxidation of thiophenol
3.10. Reaction of [Pt2(m-S)2(PPh3)4] 1 with diphenyl ditelluride in
methanol
(BDH, 0.5 mL, 5 mmol) in MeOH (5 mL) with 27% H2O2 (1 mL,
10 mmol). After 1 h the white crystalline solid was filtered, washed
with MeOH (2 Â 10 mL) and dried under vacuum (540 mg, 99%).
[Pt2(m-S)2(PPh3)4] (51 mg, 0.034 mmol) and Ph2Te2 (27 mg,
0.066 mmol) were suspended in methanol (20 mL) and the mixture
was stirred at room temperature for 48 h, giving a clear red-brown
solution. The solution was analysed by positive-ion ESI MS.
3.3. Attempted reaction of [Pt2(m-S)2(PPh3)4] 1 with
[Pt2(m-Se)2(PPh3)4] 2 in methanol
[Pt2(m-S)2(PPh3)4] (31 mg, 0.021 mmol) and [Pt2(m-Se)2(PPh3)4]
(29 mg, 0.018 mmol) were suspended in ethanol (20 mL), the mix-
ture stirred at room temperature for 12 h, and analysed by posi-
tive-ion ESI MS.
3.11. Reaction of [Pt2(m-S)2(PPh3)4] 1 with (p-EtOC6H4)2Te2 in
methanol
[Pt2(m-S)2(PPh3)4] (49 mg, 0.033 mmol) and (p-EtOC6H4)2Te2
(33 mg, 0.066 mmol) were suspended in methanol (20 mL) and
the mixture was stirred at room temperature for 24 h, giving a
clear dark-red solution. The solution was analysed by positive-
ion ESI MS.
3.4. Reaction of [Pt2(m-Se)2(PPh3)4] 2 with S8 in methanol
A mixture of [Pt2(m-Se)2(PPh3)4] (30 mg, 0.019 mmol) and S8
(5 mg, 0.020 mmol) in toluene (10 mL) and methanol (15 mL)
was stirred at room temperature for 2 h resulting in a dark red-
brown solution with a trace amount of insoluble matter. The solu-
tion was analysed by positive-ion ESI MS.
3.12. Synthesis of [{Pt(PPh3)}3(m3-Se)(m-TePh)3]PF6 13bÁPF6
[Pt2(l
-Se)2(PPh3)4]
2
(102 mg, 0.064 mmol) and Ph2Te2
3.5. Reaction of [Pt2(m-S)2(PPh3)4] 1 with elemental Se in ethanol
(51.5 mg, 0.126 mmol) were suspended in ethanol (20 mL) and
the mixture was stirred at room temperature for 48 h, giving a
clear dark-red solution. After filtration to remove trace amounts
of insoluble matter, excess NH4PF6 (160 mg, 1 mmol) was added
to the stirred filtrate producing a red-brown precipitate which
was collected by vacuum filtration, washed successively with dis-
tilled water (2 Â 10 mL) and diethyl ether (5 mL), before drying
under vacuum to give 13bÁPF6 as a dark-brown solid (43.3 mg,
47%). ESI MS (positive-ion) m/z 2065.98, 100%. Found: C 39.82, H
3.16. C72H60F6P4Pt3SeTe3 requires C 39.13, H 2.74%. Crystals suit-
able for an X-ray diffraction study were grown from an acetone/
hexane solution.
[Pt2(m-S)2(PPh3)4] (40 mg, 0.027 mmol) and Se (100 mg,
1.27 mmol) were suspended in methanol (25 mL) and the mixture
was stirred at room temperature for 48 h resulting in a black sus-
pension. Centrifugation gave a light-yellow solution which was
analysed by ESI MS.
3.6. Reaction of [Pt2(m-S)2(PPh3)4] 1 with Ph2Se2
[Pt2(m-S)2(PPh3)4] (25 mg, 0.017 mmol) and Ph2Se2 (15.5 mg,
0.05 mmol) were suspended in methanol (20 mL) and the resulting
mixture stirred at room temperature for 24 h. The cloudy yellow
mixture was filtered to remove any insoluble matter and the fil-
trate analysed by ESI MS. The reaction in ethanol was carried out
in analogous fashion, using [Pt2(m-S)2(PPh3)4] (30 mg, 0.020 mmol)
and Ph2Se2 (19 mg, 0.061 mmol).
3.13. X-ray crystallography
The diffraction data (19529 reflections; hmax = 74.0°) for a dia-
mond-like sample of [{Pt(PPh3)}3(m3-Se)(m-TePh)3]PF6 13bÁPF6
(0.16 x 0.17 0.28 mm) were measured using a SuperNova CCD
3.7. Reaction of [Pt2Se2(PPh3)4] 2 with Ph2S2 in methanol
diffractometer with Cu-K
The intensity data were processed with the CrysAlis Pro software
suite [42]; 4509 independent data (Rint = 0.040) and 4072 with
a radiation (k = 1.54184 Å) and x scans.
[Pt2(m-Se)2(PPh3)4] (25 mg, 0.016 mmol) and Ph2S2 (8.72 mg,
0.040 mmol) were suspended in methanol (20 mL) and the result-
ing mixture was stirred for 24 h. The cloudy dark-red mixture was
filtered to remove any insoluble matter and the clear dark-red fil-
trate was examined by ESI MS. The reaction in ethanol was carried
out in analogous fashion, using [Pt2(m-Se)2(PPh3)4] (50 mg,
0.031 mmol) and Ph2S2 (13 mg, 0.060 mmol).
I ꢁ 2
r(I). The structure was solved by direct methods [43] and
full-matrix least-squares refinement on F2 was performed using
SHELXL-2014/7 [44] integrated in WinGX [45]. The C-bound H
atoms were placed on stereochemical grounds and refined in the
riding model approximation with Uiso = 1.2Ueq(carrier atom). A
weighting scheme of the form w = 1/[r
2(F2o) + (0.0595P)2 +
92.592P] where P = (F2o + 2Fc2)/3 was employed in the final cycles
of refinement. Nine reflections were omitted from the final cycles
of refinement as detailed in the CIF deposited with the CCDC
(deposition number: 1520632). The maximum and minimum
residual electron density peaks of 1.51 and 1.65 e ÅÀ3, respectively,
were located 1.27 and 0.52 Å from the Te1 and P3 atoms, respec-
tively. Crystallographic diagrams were drawn with ORTEP-3 for
Windows [45] and DIAMOND [46]; PLATON [47] was also used in
the study. Crystallographic data and refinement details for
13bÁPF6: formula = C144H120F18P9Pt6Se2Te6, formula weight =
3.8. Reaction of [Pt2(m-Se)2(PPh3)4] 2 with Ph2Te2 in ethanol
[Pt2(m-Se)2(PPh3)4] (102 mg, 0.064 mmol) and Ph2Te2 (51.5 mg,
0.126 mmol) were suspended in ethanol (20 mL) and the mixture
was stirred at room temperature for 48 h, giving a clear dark-red
solution. The solution was analysed by positive-ion ESI MS.
3.9. Reaction of [Pt2(m-Se)2(PPh3)4] 2 with (p-EtOC6H4)2Te2 in ethanol
[Pt2(m-Se)2(PPh3)4] (98 mg, 0.061 mmol) and (p-EtOC6H4)2Te2
(62 mg, 0.125 mmol) were suspended in ethanol (20 mL) and the
mixture was stirred at room temperature for 24 h, giving a clear
dark-red solution. The solution was analysed by positive-ion ESI
MS.
ꢀ
2282.59, crystal system = trigonal, space group = R3 (hexagonal
setting), a = 14.6495(4) Å, c = 54.5424(17) Å, V = 10137.0(6) Å3,
, l
Z = 3, Dc = 2.243 g cmÀ3 = 23.596 mmÀ1, R (obs. data) = 0.034,
Rw (all data) = 0.093.