group P21/c, a = 18.388(3), b = 13.369(2), c = 22.436(4) Å, β = 95.41(1)Њ,
V = 5491(3) Å3, Dc = 1.75 g cmϪ1 for Z = 8, F(000) = 2816, radiation
Mo-Kα, λ = 0.71073 Å, µ(Mo-Kα) = 55.4 cmϪ1, T = 294 1 K, crystal
size = 0.10 × 0.18 × 0.50 mm, mounted on a glass fibre, Enraf-Nonius
CAD4 diffractometer, graphite monochromator, ω Ϫ 2θ scan tech-
nique, maximum 2θ = 52.0Њ; unit cell constants from the setting angles
of 25 reflections in the range 9 < θ < 14Њ, Lorentz and polarization cor-
rections, semi-empirical absorption correction based on a series of Ψ-
scans (from 0.922–1.000 on I); anisotropic decay (from 0.965 to 1.069
on I), reflection averaging R(int) = 2.1%, 11581 total reflections col-
Notes and references
† Characterization of A. Yellow solid (Found: C, 56.4; H, 4.4; N, 1.1%);
m/z (FABϪ) 356; νmax/cmϪ1 1083 vs and 1072 vs; 343 w and 330 m-w
(Pt᎐Cl); 1H and 13C{1H} NMR spectra reveal no signals other than
those due to the phosphonium cation even at high signal:noise ratios
and this observation suggests that A is a phosphonium salt of a purely
inorganic anion. All attempts to obtain X-ray quality crystals failed.
Slow evaporation of a dichloromethane solution of A over ca. one
month yielded only poor quality crystals. Dissolution of these crystals
in CH2Cl2 and repeated slow evaporation gave only a few crystals of the
well-known complex (Ph3PCH2Ph)2[Pt2(µ-Cl)2Cl4] (see ref. 2) along
with additional poor quality, yellow crystals of A.
‡ “Aged” BF3ؒOEt2 (0.22 mL, 1.77 mmol) was added to a solution of
(Ph3PCH2Ph)2[PtCl4]2 (0.19 g, 0.18 mmol) in MeNO2 (10 mL). After 30
min, the solvent was removed in vacuo at 40 ЊC. The oily residue was
washed with Et2O (30 mL), dissolved in MeOH (2 mL), filtered from
small amounts of undissolved material and Et2O (30 mL) was added to
the filtrate. A precipitate formed which was collected on a filter and
dried in air at 20–25 ЊC. Yields of (Ph3PCH2Ph)[PtCl3(C3H3NO)] after
column chromatography on SiO2 (Wako; eluent CH2Cl2 :Me2CO = 2:1,
v/v) were 10–15%. The isoxazole compound could also be separated
from A on slow evaporation of a dichloromethane solution from a long
narrow tube. The former is much less soluble in CH2Cl2 than the latter
and crystals of (Ph3PCH2Ph)[PtCl3(C3H3NO)] were separated by hand
when they appeared in the upper part of the tube.
2
lected, 11219 unique, 6334 reflections with Fo2 > 3.0σ(Fo ), solution by
direct methods,11 refinement by full-matrix least-squares, function min-
2
2
imized was Σw(|Fo| Ϫ |Fc|)2, weight w defined as 4Fo /σ2(Fo ), hydrogen
atoms included with Uiso = 1.3 × U(bonding atom), 626 refined param-
eters, R = 0.044, Rw = 0.053, S = 1.56, largest shift = 0.01σ, highest
peak in final difference map 2.49 (14) e ÅϪ3 (0.735 Å from Cl3),
low peak 0.00 (15) e ÅϪ3. Scattering factors for neutral atoms and the
values for ∆f Ј and ∆f Љ were taken from International Tables for X-ray
Crystallography;9 computer programs: MolEN.10
Atomic coordinates, bond lengths and angles, and thermal param-
eters for I and II have been deposited at the Cambridge Crystallo-
graphic Data Centre (CCDC). See ‘Instructions for Authors’, J. Chem.
Soc., Perkin Trans. 1, available via the RSC web page (http://
www.rsc.org/authors). Any request to the CDCC for this material
should quote the full literature citation and the reference number
207/251.
§ Characterization of (Ph3PCH2Ph)[PtCl3(C3H3NO)] (i) sample
obtained from MeNO2–BF3ؒOEt2 synthesis (Calc. for C28H25Cl3-
NOPPt: C, 46.46; H, 3.48; N, 1.93. Found: C, 45.62; H, 3.13; N, 1.87%);
m/z (FABϪ) 370 (Calc. 370 for [PtCl3(C3H3NO)]Ϫ); mp 147–149 ЊC; (ii)
sample obtained from independent synthesis (Calc. for C28H25Cl3-
NOPPt: C, 46.46; H, 3.48; N, 1.93. Found: C, 46.53; H, 3.50; N, 1.87%);
m/z (FABϪ) 370 (Calc. 370 for [PtCl3(C3H3NO)]Ϫ); mp 147–149 ЊC.
δH(CDCl3, J values in Hz) (signals due to C3H3NO): 6.39 (dd, JHH 2,
1H), 8.40 (d, JHH 2, 1H) and 8.69 (d, JHH 2, 1H); (signals due to
Ph3PCH2Phϩ): 5.18 (d, JPH 14, 2H), 7.0–7.2 (m, phenyl protons, 8H),
7.6–7.8 (m, phenyl protons, 16H); δC({1H}, CDCl3) (signals due to
1 J. A. Davies, C. M. Hockensmith, V. Yu. Kukushkin and Yu. N.
Kukushkin, Synthetic Coordination Chemistry: Principles and
Practice, World Scientific, Singapore–New Jersey–London, 1996.
2 V. Yu. Kukushkin, V. M. Tkachuk, I. A. Krol, Z. A. Starikova, B. V.
Zhadanov and N. P. Kiseleva, Zh. Obsch. Khim., 1991, 61, 51.
3 V. Yu. Kukushkin, I. A. Krol, Z. A. Starikova and V. M. Tkachuk,
Koord. Khim., 1990, 16, 1406.
4 W. R. Roush, in Comprehensive Organic Synthesis, eds. B. M. Trost
and I. Fleming, Pergamon Press, Oxford, 1991, vol. 5, p. 513; B. J.
Wakefield and D. J. Wright, Adv. Heterocycl. Chem., 1979, 25, 147;
N. K. Kochetkov and S. D. Sokolov, Adv. Heterocycl. Chem., 1962,
2, 365; S. A. Lang and Y.-I. Lin, in Comprehensive Heterocyclic
Chemistry, ed. K. T. Potts, vol. 6, Pergamon Press, New York, 1984,
p. 1; P. Grunanger and P. Via-Finzi, Isoxazoles, in Chemistry of
Heterocyclic Compounds, vol. 49, part 1, Wiley Interscience,
New York, 1991, pp. 877.
5 K. J. Oliver, T. N. Waters, D. F. Cook and C. E. F. Rickard, Inorg.
Chim. Acta, 1977, 24, 85; G. Pelizzi, Transition Met. Chem., 1979, 4,
199; C. K. Schauer, O. P. Anderson, N. R. Natale and D. A. Quincy,
Acta Crystallogr., Sect. C, 1986, 42, 884.
6 M. S. Munsey and N. R. Natale, Coord. Chem. Rev., 1991, 109, 251;
a search of the Cambridge Structural Database revealed no other
structural data of isoxazole complexes of the platinum group
metals.
7 M. Biddau, G. Devoto, M. Massacesi and G. Ponticelli, Transition
Met. Chem., 1976, 1, 99; I. A. Zakharova, Ja. V. Salyn, L. V.
Tatjanenko, Yu. Sh. Mashkovsky and G. Ponticelli, J. Inorg. Bio-
chem., 1981, 15, 89; G. Ponticelli, personal communication, 1997.
8 P. Main, S. J. Fiske, S. E. Hull, L. Lessinger, G. Germain, J. P.
DeClerg and M. M. Woolfson, MULTAN80, University of York,
UK, 1980.
9 International Tables for X-ray Crystallography, vol. IV, Kynoch
Press, Birmingham, 1974 (Present distributor: Kluwer Academic
Publishers, Dordrecht).
10 C. K. Fair, MolEN, An Interactive Intelligent System for Crystal
Structure Analysis, User Manual, Enraf-Nonius, Delft, The
Netherlands, 1980.
11 M. C. Burla, M. Camalli, G. Cascarano, C. Giacovazzo, G. Polidori,
R. Spagna and D. Viterbo, SIR, J. Appl. Crystallogr., 1989, 22, 389.
C3H3NO): 106.3, 149.4 and 158.8; νmax/cmϪ1 1552 m (C᎐N), 336 s and
᎐
322 sh (Pt–Cl).
¶ Isoxazole (0.33 mL, 5.16 mmol; Aldrich) was added at room temper-
ature to a solution of (Ph3PCH2Ph)2[Pt2(µ-Cl)2Cl4] (0.34 g, 0.26 mmol)
in DMF (2 mL). The reaction mixture was left to stand for 3 h at 20–
25 ЊC, then Et2O (40 mL) was added to give an oily residue. After
decanting of the solvent, methanol (3 mL) was added and the residue
rapidly crystallized on stirring the mixture. The yellow precipitate was
collected on a filter, washed twice with 1 mL portions of MeOH and
three times with 3 mL portions of Et2O, and dried in air at 20–25 ЊC.
Yield of (Ph3PCH2Ph)[PtCl3(C3H3NO)]: 0.19 g, 50%.
|| Crystal data for I: C28H25Cl3NOPPt, Mr = 723.94; monoclinic, space
group Cc, a = 9.451(1), b = 27.882(3), c = 10.882(2) Å, β = 106.55(1)Њ,
V = 2749(1) Å3, Dc = 1.75 g cmϪ1 for Z = 4, F(000) = 1408, radiation
Mo-Kα, λ = 0.71073 Å, µ(Mo-Kα) = 55.3 cmϪ1, T = 294 1 K, crystal
size = 0.12 × 0.20 × 0.30 mm, mounted on a glass fibre, Enraf-Nonius
CAD4 diffractometer, graphite monochromator, ω Ϫ 2θ scan tech-
nique, maximum 2θ = 52.0Њ, unit cell constants from the setting angles
of 25 reflections in the range 10 < θ < 14Њ, Lorentz and polarization
corrections, semi-empirical absorption correction based on a series of
Ψ-scans (from 0.640–1.000 on I), anisotropic decay (from 0.961 to
1.030 on I), 2938 total reflections collected, 2938 unique, 2639 reflec-
tions with Fo2 > 3.0σ(Fo ), solution by direct methods,8 refinement by
2
full-matrix least-squares, function minimized was Σw(|Fo| Ϫ |Fc|)2,
weight w defined as 4Fo /σ2(Fo ), hydrogen atoms included with
Uiso = 1.3 × U(bonding atom), 314 refined parameters, R = 0.035,
Rw = 0.050, S = 1.77, largest shift = 0.01σ highest peak in final differ-
ence map 0.98 (15) e ÅϪ3, low peak Ϫ0.23 (15) e ÅϪ3. Scattering factors
for neutral atoms and the values for ∆f Ј and ∆f Љ were taken from
International Tables for X-ray Crystallography;9 computer programs:
MolEN.10
2
2
Communication 8/06251J
Crystal data for II: C28H25Cl3NOPPt, Mr = 723.94; monoclinic, space
3140
J. Chem. Soc., Perkin Trans. 1, 1998, 3139–3140