3974 Organometallics, Vol. 23, No. 16, 2004
Fornie´s et al.
(m, 8H, CH2). 19F NMR (HDA, rt): -112.3 (d, 2F, o-F, J Pt-F
407.0 Hz), -115.1 (br, 2F), -162.5 (m, 1F, p-F), -163.3 (m,
2F, m-F), -163.7 ppm (m, 1F, p-F), -165.0 (m, 2F, m-F).
m-F + p-F). Crystals suitable for X-ray diffraction analysis
were obtained by slow diffusion of a layer of n-hexane (20 mL)
into a solution of 25 mg of 1 in 5 mL of Me2CO at 4 °C.
R ea ct ion of [NBu 4]2[P t (C6Cl5)4] w it h [Cd (cyclen )-
(MeOH)2](ClO4)2. [NBu4]2[Pt(C6Cl5)4] (0.25 g, 0.146 mmol) was
added to a MeOH (10 mL) solution of [Cd(cyclen)(MeOH)2]-
(ClO4)2 (0.146 mmol) prepared in situ. After 1 h of stirring the
solution was evaporated to dryness. Treatment of the resulting
)
Syn th esis of [P t(C6F 5)2Cl2Cd (cyclen )]2 (4). [NBu4]2[Pt2-
(µ-Cl)2(C6F5)4] (0.23 g, 0.146 mmol) was added to a MeOH (10
mL) solution of [Cd(cyclen)(MeOH)2](ClO4)2 (0.146 mmol)
prepared in situ. The resulting white suspension was stirred
for 1 h, and then the white solid was filtered off. This solid
was washed with CHCl3 (2 × 3 mL) and n-hexane (5 mL) and
vacuum-dried (4, 29% yield). Anal. Calcd (%) for C40H40F20N4-
Cl4Cd2Pt2: C 27.13, H 2.26, N 6.33. Found: C 27.28, H 2.23,
N 6.27. IR (Nujol): ν 810, 799 cm-1 (s; C6F5, X-sensitive vibr.).27
1H NMR (HDA, rt): 3.50 (br, 4H, N-H), 3.16 (m, 8H), 2.90
i
white residue with PrOH (30 mL) produced a solid that was
filtered and identified as the starting material [NBu4]2[Pt(C6-
Cl5)4].
Rea ction of [NBu 4]2[P d (C6F 5)4] w ith [Cd (cyclen )(Me-
OH)2](ClO4)2. [NBu4]2[Pd(C6F5)4] (0.18 g, 0.146 mmol) was
added to a MeOH (10 mL) solution of [Cd(cyclen)(MeOH)2]-
(ClO4)2 (0.146 mmol) prepared in situ. After 1 h of stirring at
room temperature the solution was evaporated to dryness.
ppm (m, 8H). 19F NMR (HDA, rt): -115.2 (d, 8F, o-F, J Pt-F
)
528.2 Hz), -162.1 ppm (m, 4F, p-F), -163.0 ppm (m, 8F, m-F).
Crystals suitable for X-ray diffraction analysis were obtained
by slow diffusion of a layer of n-hexane (20 mL) into a solution
of 25 mg of 4 in 5 mL of Me2CO at 4 °C.
i
Treatment of the resulting white residue with PrOH (30 mL)
produced a solid that was filtered and identified mostly as the
starting material [NBu4]2[Pd(C6F5)4], along with some small
fractions of decomposition products, which we were not able
to identify.
Syn th esis of [Cd 2(µ-Cl)2(cyclen )2](ClO4)2 (5). (NBu4)Cl
(0.08 g, 0.290 mmol) was added to a MeOH (10 mL) solution
of [Cd(cyclen)(MeOH)2](ClO4)2 (0.290 mmol) prepared in situ,
and the precipitation of a white solid is observed almost
immediately. This white solid was filtered off and vacuum-
dried (5, 52% yield). Anal. Calcd (%) for C16H40Cl4N8O8Cd2: C
Syn th esis of [(C6F 5)2(CtCP h )2P tCd (cyclen )] (2). To a
white suspension of [PMePh3]2[Pt(C6F5)2(CtCPh)2] (0.25 g,
0.194 mmol) in MeOH (60 mL) were added cyclen (0.033 g,
0.194 mmol) and CdClO4‚6H2O (0.081 g, 0.194 mmol) to give
a pale yellow solution. Immediately a very pale yellow solid
started forming. After 15 min of stirring, the pale yellow solid
was filtered (0.076 g). By evaporation to a small volume of the
solvent (∼10 mL) a second fraction was obtained (0.034 g) (44%
yield). Anal. Calcd (%) for C36H30F10N4CdPt: C 42.55, H 2.98,
N 5.51. Found: C 42.34, H 2.74, N 5.33; IR (Nujol): ν 2097
(vs), 2080 (sh) cm-1 (CtC); 766, 758 cm-1 (s; C6F5, X-sensitive
vibr.).27 ΛM ) 3.3 (acetone) Ω-1 cm2 mol-1. 1H NMR (HDA, rt):
aromatics: 7.29 (m, 4H), 7.19 (m, 6H); cyclen ligand: 3.13 (br,
4H, N-H), 2.95 (m, 8H), 2.86 ppm (m, 8H). 19F NMR (HDA,
rt): -116.0 (d, 4F, o-F, J Pt-F ) 348.1 Hz), -166.5 ppm (m, 6F,
p-F + m-F); at 190 K: -115.5 (d, 1F, o-F, J o-F-m-F ) 30 Hz,
1
22.88, H 4.77, N 13.25. Found: C 23.33, H 5.32, N 13.50. H
NMR (DMSO, rt): 2.62 (br, 4H, N-H), 2.49 (m, 16H).
X-r a y Str u ctu r e Deter m in a tion s. Crystal data and other
details of the structure analyses are presented in Table 1.
Crystals were mounted at the end of a quartz fiber. The
radiation used in all cases was graphite-monochromated Mo
KR (λ ) 0.71073 Å).
For 1‚2Me2CO, 3‚0.5MeOH, 4‚2Me2CO, and 5, hemispheres
of X-ray intensity data were collected on a Bruker SMART
APEX diffractometer. An absorption correction was applied on
the basis of 3219, 4477, 3132, and 1696 symmetry equivalent
reflection intensities, respectively. For 2‚2Me2CO, X-ray in-
tensity data were collected with a NONIUS κCCD area-
detector diffractometer. Images were processed using the
DENZO and SCALEPACK suite of programs.28 The absorption
correction was performed using SORTAV.29
The structures, except 2‚2Me2CO, were solved by Patterson
and Fourier methods using the program SHELXS-97.30 The
structure of 2‚2Me2CO was solved using the DIRDIF9231
program. The structures were refined by full-matrix least
squares on F2 with SHELXL-97. All non-hydrogen atoms were
assigned anisotropic displacement parameters and refined
without positional constraints except as noted below. All
hydrogen atoms were constrained to idealized geometries and
assigned isotropic displacement parameters equal to 1.2 times
the Uiso values of their attached parent atoms (1.5 times that
for the methyl hydrogen atoms). In the structure of 2‚2Me2-
CO, two molecules of the crystallization solvent were found
in the asymmetric unit. One of the acetone molecules was
found to be disordered, and to model this molecule, the
O(100)-C(90) distance was constrained to 1.2(0.01) Å, while
the methyl carbon atoms (C(92), C(91)) were constrained to a
distance of 1.50(0.01) of the carbonyl carbon atom C(90). In
the structure of 3‚0.5MeOH, a molecule of MeOH, one of the
solvent molecules used for the preparation of the complex, was
found and refined with partial occupancy of 0.5. The OH
hydrogen atom of the methanol moiety was not added to the
model. In the structures of 2‚2Me2CO, 4‚2Me2CO, and 5, the
J Pt-F ) 422 Hz), -116.0 (d, 1F, o-F, J o-F-m-F ) 30 Hz, J Pt-F
≈
315 Hz), -116.3 (d, 1F, o-F, J o-F-m-F ) 26 Hz, J Pt-F ≈ 315
Hz), -117.5 (d, 1F, o-F, J o-F-m-F ) 26 Hz, J Pt-F ) 420 Hz),
-165.86, -165.97, -166.0 ppm (2p-F + 4m-F). Crystals
suitable for X-ray diffraction analysis were obtained by slow
evaporation of a saturated solution of 2 in Me2CO at 20°C.
Syn th esis of [NBu 4][P t(C6F 5)2(bzq)] (6). A 1,2-dichloro-
ethane (20 mL) solution of [NBu4][Pt(C6F5)3(bzq)] was refluxed
for 3 h. After this time, the solution is allowed to reach room
temperature and was evaporated to dryness and the orange
i
residue treated with PrOH (10 mL) and filtered off, washed
with n-hexane (5 mL), and vacuum-dried (63% yield). Anal.
Calcd (%) for C51H36F10NPt: C 51.80, H 4.64, N 2.94. Found:
C 51.14, H 4.07, N 2.83. IR (Nujol): ν 766, 796 cm-1 (s; C6F5,
X-sensitive vibr.).27 1H NMR (HDA, rt): 7,8-benzoquinolinate
ligand: 7.80 (m, 6H), 8.50 (d, 1H), 8.67 (d, 1H J Pt-H ) 33.6
+
Hz); NBu4 1.00 (t, 12H, CH3), 1.45 (q, 8H, γ-CH2), 1.77 (m,
8H, â-CH2), 3.45 (m, 8H, R-CH2). 19F NMR (HDA, rt): -112.1
(d, 2F, o-F, J Pt-F ) 360.6 Hz), -112.4 (d, 2F, o-F, J Pt-F ) 651.0
Hz), -163.6 (m, 2F, m-F), -166.2 (m, 2F, m-F), -164.5 ppm
(m, 1F, p-F), -167.2 (m, 1F, p-F).
Syn th esis of [(C6F5)2(bzq)P tCd(cyclen )](ClO4) (3). [NBu4]-
[Pt(C6F5)2(bzq)] (0.083 g, 0.087 mmol) was added to a MeOH
(8 mL) solution of [Cd(cyclen)(MeOH)2](ClO4)2 (0.087 mmol)
prepared in situ. After a few minutes, a yellow solid precipi-
tated from the yellow solution. The resulting suspension was
stirred for 1 h, and then the yellow solid was filtered off. This
solid was washed with n-hexane (5 mL) and vacuum-dried (3,
50% yield). Anal. Calcd (%) for C33H28F10N5O4ClCdPt: C 36.28,
H 2.56, N 6.41. Found: C 36.11, H 2.39, N 6.39. IR (Nujol): ν
776, 801 cm-1 (s; C6F5, X-sensitive vibr.).27 ΛM ) 81 (acetone)
(28) Otwinowski Z.; Minor, W. Methods Enzymol. A: Macromol.
Crystallogr. 1997, 276, 307.
(29) Blessing, R. H. Acta Crystallogr., Sect. A 1995, 51, 33.
(30) Sheldrick, G. M. SHELX-97, a program for the refinement of
crystal structures; University of Go¨ttingen, Germany, 1997.
(31) Beursken. P. T.; Beursken, G.; Bosman, W. P.; de Gelser, R.;
Garc´ıa Granda, S.; Gould, R. O.; Smith J . M. M.; Smykalla, C. The
DIRDIF92 program system, Technical Report of the Crystallography
Laboratory; 1992.
Ω-1 cm2 mol-1 1H NMR (HDA, rt): 7,8-benzoquinolinate
.
ligand: 7.83 (m, 6H), 8.80 (d, 1H), 8.95 (d, 1H J Pt-H ) 23.7
Hz); cyclen ligand: 2.26 (br, 4H, NH), 2.42 (m, 8H, CH2), 2.57