Heteropolynuclear Benzoquinolateplatinum(II) Complexes
Organometallics, Vol. 25, No. 18, 2006 4339
(C6F5)3].38 C, H, and N analyses and mass, IR, and NMR spectra
were performed as described elsewhere.38 Molar conductances were
carried out on a Philips PW9509 conductimeter in acetone and
dichloromethane solutions (5 × 10-4 M). The optical absorption
spectra were recorded using a Hewlett-Packard 8453 (solution)
spectrophotometer in the visible and near-UV ranges. Emission and
excitation spectra were obtained on a Perkin-Elmer LS 50B
luminescence spectrometer and on a Jobin-Ybon Horiba Fluorolog
3-22 Tau-3 spectrofluorimeter, with the lifetime measured in
phosphorimeter mode.
Safety Note: Perchlorate salts of metal complexes with organic
ligands are potentially explosive. Only small amounts of material
should be prepared, and these should be handled with great caution.
Preparation of [NBu4][Pt(bzq)(C6Cl5)2] (2). To a solution of
[NBu4][Pt(C6Cl5)3(tht)] (0.300 g, 0.223 mmol) in toluene (10 mL)
was added Hbzq (0.084 g, 0.471 mmol). After 6 h of reflux the
existence of a green solid was observed. This solid was then filtered
off, washed with iPrOH and n-hexane, and finally air-dried (0.080
g, 30% yield). Anal. Found: C, 43.85; H, 4.46; N, 2.56. C41H44-
Cl10N2Pt requires: C, 44.17; H, 3.98; N, 2.51. IR (KBr): ν ) 822
(m, C6Cl5, X-sensitive vibr.).72 1H NMR (acetone-d6, rt): 0.84 (t,
12H, (N(CH2CH2CH2CH3)+), 1.31 (sext., 8H, (N(CH2CH2CH2-
CH3)+), 1.67 (m, 8H, (N(CH2CH2CH2CH3)+), 3.29 (m, 8H, (N(CH2-
CH2CH2CH3)+), 6.94 (dd, 1H, J(195Pt-H) ) 40.8 Hz), 7.17 (t, 1H),
7.33 (m, 2H), 7.50 (d, 1H), 7.63 (d, 1H), 8.34 (dd, 1H), 7.94 ppm
(dd, 1H, J(195Pt-H) ) 24.0 Hz).
Preparation of [NBu4][{Pt(bzq)(C6F5)2}2Ag] (3). To a yellow
solution of [NBu4][Pt(bzq)(C6F5)2] (0.050 g, 0.053 mmol) in acetone
(6 mL) was added AgClO4 (0.005 g, 0.026 mmol). After 1 h of
stirring in the absence of light the solution was concentrated to ca.
3 mL, and a layer on n-hexane was deposited above. Slow diffusion
of this n-hexane into the concentrated solution gave yellow crystals.
These crystals were filtered off and air-dried, allowing evaporation
of the crystallization solvents (0.017 g, 37% yield). Anal. Found:
C, 44.89; H, 3.02; N, 2.40. C66H52AgF20N3Pt2 requires: C, 44.91;
H, 2.97; N, 2.38. IR (Nujol): ν ) 1632 (w), 1562 (w), 1495 (s),
1057 (s), 1043 (m), 955 (s), 888 (w), 831 (m), 820 (w), 800 (m,
C6F5, X-sensitive vibr.),72 777 cm-1 (m, C6F5, X-sensitive vibr.).72
1H NMR (CD2Cl2, rt): 1.00 (t, 12H, (N(CH2CH2CH2CH3)+), 1.45
(m, 8H, (N(CH2CH2CH2CH3)+), 1.81 (m, 8H, (N(CH2CH2CH2-
CH3)+), 3.44 (m, 8H, (N(CH2CH2CH2CH3)+), 7.02 (b, 4H), 7.31
(dd, 2H), 7.55 (m, 6H), 8.26 (dd, 2H, J(195Pt-H) ) 27.5 Hz), 8.51
ppm (dd, 2H). 19F NMR (CD2Cl2, rt): -112.1 (b, 1F, o-F), -114.5
(b, 1F, o-F), -115.3 (d, 1F, o-F), -116.4 (m, 2F, o-F), -116.6 (b,
1F, o-F), -118.2 (d, 1F, o-F), -118.6 (d, 1F, o-F), -164.5 (m,
4F, m-F + p-F), -165.4 ppm (m, 3F, m-F + p-F), -166.0 ppm
(m, 3F, m-F + p-F), -166.4 ppm (m, 2F, m-F). 19F NMR (acetone-
d6, rt): -113.2 (b, 4F, o-F, J(195Pt-F) ) 546.7 Hz), -115.5 (b,
4F, o-F, J(195Pt-F) ) 314.0 Hz), -164.8 (m, 6F, m-F + p-F),
-166.2 ppm (m, 6F, m-F + p-F).
NMR (CDCl3, -60°C): 6.98 (m, 6H), 7.44 (m, 6H), 7.47 (m, 4H),
7.58 (t, 1H), 7.72 (m, 2H), 7.80 (d;1H), 8.37 (d, 1H), 8.64 ppm (d,
1H). 19F NMR (CDCl3, rt): -115.2 (d, 2F, o-F, J(195Pt-F) ) 538.3
Hz), -118.4 (d, 2F, o-F, J(195Pt-F) ) 344.0 Hz), -161.8 (t, 1F,
p-F), -163.8 (m, 3F, m-F + p-F), -163.8 ppm (m, 2F, m-F). 19F
NMR (CDCl3, -60 °C): -113.8 (d, 1F, o-F, J(195Pt-F) ) 597.6
Hz), -116.0 (d, 1F, o-F, J(195Pt-F) ) 378.7 Hz), -118.9 (d, 2F,
o-F, J(195Pt-F) ) 313.8 Hz), -161.9 (t, 1F, p-F), -163.1(m, 3F,
m-F + p-F), -164.5 ppm (m, 2F, m-F). 31P NMR (CDCl3, -60
°C): 13.0 ppm (J(109Ag-P) ) 733.3, J(107Ag-P) ) 637.8, J(195Pt-
P) ) 228 Hz).
Preparation of [{Pt(bzq)(C6Cl5)2}Ag(PPh3)] (5). To a yellow
solution of [NBu4][Pt(bzq)(C6Cl5)2] (0.080 g, 0.007 mmol) in CH2-
Cl2 (15 mL) was added [Ag(OClO3)(PPh3)] (0.034 g, 0.072 mmol).
After 1 h of stirring in the absence of light the solution was
evaporated to dryness. The residue was treated with OEt2 (15 mL),
and a white solid (NBu4ClO4) was filtered off. The yellow solution
was evaporated to dryness, and the residue was treated with
n-hexane, filtered off, and finally air-dried (0.026 g, 29% yield).
Anal. Found: C, 41.56; H, 1.82; N, 0.90. C43H23AgCl10NPPt
requires: C, 41.58; H, 1.87; N, 1.13. IR (KBr): ν ) 1622 (w),
1479 (m), 1435 (s), 1326 (s), 1315 (s), 1289 (vs), 1261 (m), 1213
(s), 1097 (vs), 833 (s), 819 (m, C6Cl5, X-sensitive vibr.),72 741 (s),
1
722 (m), 692 (s), 671 (s), 624 (m), 5,21 (s), 508 cm-1 (m). H
NMR (acetone-d6, rt): 6.66 (m, 6H), 7.16 (m, 6H), 7.34 (m, 5H),
7.44 (dd, 1H), 7.54 (d, 1H), 7.66 (d, 1H), 7.69 (d, 1H), 8.32 (dd,
1H), 8.56 ppm (dd, 1H, J(195Pt-H) ) 16.4 Hz). 31P NMR (acetone-
d6, rt): 10.4 ppm (J(109Ag-P) ) 727.0, J(107Ag-P) ) 635.0,
J(195Pt-P) ) 236 Hz).
X-ray Structure Determinations. Crystal data and other details
of the structure analyses are presented in Table 5 (full data for the
X-ray analyses of 3a at 100 and 293 K are presented in the SI).
Suitable crystals for X-ray diffraction studies were obtained by slow
diffusion of n-hexane into concentrated solutions of the complexes
in 3 mL of Me2CO (3a and 3b) or CHCl3 (4‚CHCl3‚0.5n-C6H14
and 5‚0.58CHCl3‚0.25n-C6H14). 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 3a and 3b, X-ray intensity data were collected with a Nonius
κCCD area-detector diffractometer. Images were processed using
the DENZO and SCALEPACK suite of programs.73 The absorption
correction was performed using SORTAV.74 For 4‚CHCl3‚0.5n-
C6H14, X-ray intensity data were collected on a Bruker Smart Apex
diffractometer. The diffraction frames were integrated using the
SAINT program.75 For 5‚0.58CHCl3‚0.25n-C6H14, X-ray intensity
data were collected on an Oxford Diffraction Xcalibur diffracto-
meter. The diffraction frames were integrated using the CrysAlis
RED program.76 Both sets of data were corrected for absorption
with SADABS.77
The structures were solved by Patterson and Fourier methods
and refined by full-matrix least squares on F2 with SHELXL-97.78
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
for the methyl hydrogen atoms). In the structure of 5‚0.58CHCl3‚
0.25n-C6H14, a CHCl3 and half an n-hexane molecule were found
Preparation of [{Pt(bzq)(C6F5)2}Ag(PPh3)] (4). To a yellow
solution of [NBu4][Pt(bzq)(C6F5)2] (0.200 g, 0.210 mmol) in CH2-
Cl2 (30 mL) was added [Ag(OClO3)(PPh3)] (0.099 g, 0.210 mmol).
After 1 h of stirring in the absence of light the solution was
evaporated to dryness. The residue was treated with OEt2 (20 mL),
and a white solid (NBu4ClO4) was filtered off. The yellow solution
was evaporated to dryness, and the residue was treated with
n-hexane, filtered off, and finally air-dried (0.175 g, 77% yield).
Anal. Found: C, 47.66; H, 2.26; N, 1.37. C43H23AgF10NPPt
requires: C, 47.93; H, 2.15; N, 1.30. IR (Nujol): ν ) 1632 (w),
1500 (s), 1098 (m), 1060 (s), 1044 (m), 955 (s), 836 (m), 821 (w),
801 (m, C6F5, X-sensitive vibr.),72 777 (m, C6F5, X-sensitive vibr.),72
(73) Otwinowski, Z.; Minor, W. Methods Enzymol. A: Macromol.
Crystallogr. 1997, 276, 307.
(74) Blessing, R. H. Acta Crystallogr., Sect. A 1995, 51, 33.
(75) SAINT; Siemens Analytical X-ray Instruments Inc: Madison, WI,
1994.
(76) CrysAlis RED; Oxford Diffraction: Oxford, UK, 2004.
(77) Sheldrick, G. M. SHELXL-94; University of Go¨ttingen: Germany,
1994.
1
742 (s), 692 (s), 522 (m), 505 cm-1 (m). H NMR (CDCl3, rt):
6.94 (m, 7H), 7.28 (m, 10H), 7.41 (m, 2H), 7.63 (d, 1H), 7.81 (d,
1
1H), 8.35 (d, 1H), 8.70 ppm (d, 1H, J(195Pt-H) ) 21.6 Hz). H
(72) Maslowsky, E. J. Vibrational Spectra of Organometallic Compound;
Wiley: New York, 1977.
(78) Sheldrick, G. M. SHELXL-97; University of Gottingen: Germany,
1997.