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N.V. Kirij et al. / Journal of Organometallic Chemistry 691 (2006) 2679–2685
H3PO4 (85%); 77Se: Me2Se; 125Te: Me2Te; 195Pt: Na2PtCl6).
Acetone-d6 was used as an external lock (5 mm tube) in
reaction control measurements while an original sample
of the reaction mixture was measured in a 4 mm insert.
HMBC technique was employed to determine the 195Pt
chemical shifts and to locate the ECF3 (E = Se, Te) groups
in the 77Se and 125Te NMR spectra. Coupling patterns were
calculated using the program gNMR [41].
position of the crude material was determined (19F and 31
P
NMR) to consist of ꢂ95% cis-Pt(SeCF3)2(PPh3)2 and ꢂ5%
trans-Pt(SeCF3)2(PPh3)2 in the case of the selenium deriva-
tive and exclusively of cis-Pt(TeCF3)2(PPh3)2 for the tellu-
rium compound. In both cases, re-crystallisation from
MeCN (ꢀ21 ꢁC) gave yellow or orange crystals of the cis
derivatives in approximately 90% yields.
cis-Pt(SeCF3)2(PPh3)2. M.p. 196–197 ꢁC (dec.). Anal.
Calc. for C38H30P2F6Se2Pt: C, 44.94; H, 2.98. Found: C,
45.38; H, 3.00%.
3.2. X-ray crystal structure determinations
cis-Pt(TeCF3)2(PPh3)2. M.p. 158–159 ꢁC (dec.). Anal.
Calc. for C38H30P2F6Te2Pt: C, 41.01; H, 2.72. Found: C,
40.72; H, 2.73%.
Single crystals were grown from saturated acetonitrile
(1, 2) or dichloromethane (3) solutions of the crude mate-
rials at ꢀ21 ꢁC. All compounds cis-Pt(SeCF3)2(PPh3)2 (1),
cis-Pt(TeCF3)2(PPh3)2 (2), and trans-Pt(SeCF3)2(PPh3)2
(3) form yellow single crystals which were sealed in glass
capillaries and the suitability was checked with the help
of an IP-diffractometer (STOE IPDS II). The same device
was used to collect the reflection data of the respective best
specimen using graphite-monochromated Mo Ka radiation
3.5. Synthesis of trans-Pt(SeCF3)2(PPh3)2
Dissolution of 0.50 g (0.5 mmol) cis-Pt(SeCF3)2(PPh3)2
in 10 mL CH2Cl2 in an open beaker at ambient tem-
perature afforded quantitatively yellow crystals of trans-
Pt(SeCF3)2(PPh3)2 Æ 2CH2Cl2 (0.59 g; 0.5 mmol) upon
crystallization at room temperature over a period of 60 h.
The crystals loose CH2Cl2 upon storing in ambient atmo-
sphere for several weeks.
trans-Pt(SeCF3)2(PPh3)2. M.p. 216–218 ꢁC (dec.). Anal.
Calc. for C38H30P2F6Se2Pt: C, 44.94; H, 2.98. Found: C,
45.15; H, 3.22%.
˚
(0.71073 A). The data were corrected for Lorentz and
polarization effects. A numerical absorption correction
based on crystal-shape optimization was applied for all
data [42]. The programs used are Stoe’s X-AREA [43], includ-
ing X-RED and X-SHAPE for data reduction and absorption
correction [44], and the WINGX suite of programs [45],
including SIR-92 [46] and SHELXL-97 [47] for structure solu-
tion and refinement. All hydrogen atoms were placed in
idealized positions and constrained to ride on their parent
atom. The last cycles of refinement included atomic posi-
tions for all the atoms, anisotropic thermal parameters
for all the non-hydrogen atoms and isotropic thermal
parameters for all of the hydrogen atoms.
Acknowledgement
This work was generously supported by the Deutsche
Forschungsgemeinschaft (436 UKR 113).
References
3.3. Synthesis of cis-Pt(ECF3)Cl(PPh3)2 (E = Se, Te)
[1] For example: M. Blochmann, Chem. Vap. Deposit. 2 (1996) 85.
[2] For example: P.J. Blower, J.R. Dilworth, Coord. Chem. Rev. 76
(1987) 121.
[3] W. Tyrra, D. Naumann, B. Hoge, Yu.L. Yagupolskii, J. Fluorine
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[4] W. Tyrra, D. Naumann, Yu.L. Yagupolskii, J. Fluorine Chem. 123
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[5] W. Tyrra, N.V. Kirij, D. Naumann, Yu.L. Yagupolskii, J. Fluorine
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[6] N.V. Kirij, W. Tyrra, D. Naumann, Yu.L. Yagupolskii, I. Panten-
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[7] D. Naumann, W. Tyrra, S. Quadt, S. Buslei, I. Pantenburg, M.
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[8] N.V. Kirij, W. Tyrra, D. Naumann, I. Pantenburg, Yu.L. Yagupol-
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To a solution of 0.79 g (1.0 mmol) cis-PtCl2(PPh3)2 in
10 mL CH2Cl2 0.24 g (1.1 mmol) [NMe4]SeCF3 were added
at room temperature. The mixture was stirred for 3 h
wherein the colour changed from nearly colourless into
bright yellow. [NMe4]Cl which has precipitated was filtered
off and the crude material dried. Analysis by 19F and 31P
NMR spectroscopic methods revealed a composition of
85% cis-Pt(SeCF3)Cl(PPh3)2 and 15% cis-Pt(SeCF3)2-
(PPh3)2. The analogous reaction with [NMe4]TeCF3
(0.30 g; 1.1 mmol) carried out in MeCN gave a product
mixture of 80% cis-Pt(TeCF3)Cl(PPh3)2, 6% cis-Pt(TeCF3)2-
(PPh3)2 and 14% cis-PtCl2(PPh3)2.
[9] M.S. Hannu-Kuure, J. Komulainen, R. Oilunkaniemi, R.S. Laitinen,
´
R. Suontamo, M. Ahlgren, J. Organomet. Chem. 666 (2003) 111, and
literature cited therein.
3.4. Synthesis of cis-Pt(ECF3)2(PPh3)2 (E = Se, Te)
[10] V.P. Ananikov, I.P. Beletskaya, G.G. Aleksandrov, I.L. Emerenko,
Organometallics 22 (2003) 1414.
In
a similar manner as described above, 0.48 g
[11] R. Oilunkaniemi, R.S. Laitinen, M. Ahlgre´n, J. Organomet. Chem.
587 (1999) 200.
(2.2 mmol) [NMe4]ECF3 (E = Se, Te (0.60 g; 2.2 mmol))
were added to a suspension of 0.79 g (1.0 mmol) cis-PtCl2-
(PPh3)2 in 10 mL MeCN at room temperature. The mix-
tures were stirred for 60 min and became orange. [NMe4]Cl
was filtered off and the crude material was dried. The com-
´
[12] R. Oilunkaniemi, R.S. Laitinen, M. Ahlgren, J. Organomet. Chem.
623 (2001) 168.
[13] H. Kuniyasu, A. Maruyama, H. Kurosawa, Organometallics 17
(1998) 908.