J = 8), 8.44 (d, 1H, J = 8.5 Hz), 8.11 (s, 2H), 8.08 (t, 1H), 8.05 (t,
1H) and 7.84 (dd, 1H). FAB-MS: m/z = 384 (C25H13N5 requires
383).
J = 9), 8.57 (t, 1H), 8.50 (d, 1H, J = 9), 8.25 (d, 1H, J = 5.5),
8.00 (t, 2H), 7.67 (dd, 1H), 7.59 (d, 2H, J = 7.5), 7.51 (t, 1H),
7.40 (m, 3H), 7.35 (d, 2H, J = 5), 7.27 (t, 2H), 7.16 (t, 2H) and
7.05 (d, 2H, J = 8 Hz).
ptp. This compound was synthesized in an identical manner
to that described for pta, with 0.95 mmol, 0.198 g phenan-
threne-5,6-dione in place of acenaphthenequinone. Yield
0.291 g, 75% (Found: C, 75.60; H, 4.14; N, 16.38. Calc. for
C27H15N5ؒH2O: C, 75.88; H, 3.98; N, 16.39%). 1H NMR
[(CD3)2SO]: δ 9.45 (d, 1H, J = 6), 9.44 (d, 1H, J = 6.5), 9.23 (d,
1H, J = 6), 9.05 (d, 1H, J = 8.5), 8.90 (d, 2H, J = 8), 8.80 (d, 1H,
J = 8.5), 8.55 (d, 1H, J = 8.5 Hz), 8.12 (s, 2H), 8.05 (t, 1H), 8.00
(t, 1H), 7.94 (t, 2H) and 7.85 (dd, 1H). FAB-MS: m/z = 410
(C27H15N5 requires 409).
[Ru(tpy)(pta)][ClO4]2 5. This complex (dark brown) was
synthesized in an identical manner to that described for [Ru-
(tpy)(dppt)][ClO4]2, with 0.227 mmol, 0.087 g pta in place of
dppt. Yield 0.106 g, 51%. Single crystals suitable for an X-ray
crystallographic study were grown from acetonitrile–toluene
(1 : 1, v/v) at room temperature (Found: C, 53.0; H, 2.6; N, 13.4.
Calc. for C40H24Cl2N8O8RuؒCH3CN: C, 52.7; H, 2.8; N, 13.2%).
MS [ESMS (CH3OH)]: m/z 817 ([M Ϫ ClO4]ϩ) and 358
([M Ϫ 2ClO4]2ϩ). 1H NMR [(CD3)2SO]: δ 9.28 (d, 1H, J = 8.5),
9.15 (dd, 3H), 8.83 (d, 2H, J = 8), 8.70 (m, 4H), 8.49 (d, 2H,
J = 8), 8.41 (d, 1H, J = 8), 8.19 (d, 1H, J = 5), 8.07 (t, 2H), 7.98
(t, 2H), 7.89 (t, 1H), 7.67 (dd, 1H), 7.34 (d, 2H, J = 5 Hz) and
7.13 (t, 2H).
[Ru(dppt)2][ClO4]2 1. A mixture of dppt (0.15 g, 0.367 mmol)
and RuCl3ؒ3H2O (0.048 g, 0.183 mmol) in absolute ethanol
(30 cm3) was refluxed for 10 h. After being cooled to room
temperature, the reaction mixture was filtered. Excess of
NaClO4 in ethanol was added to the filtrate. The brownish red
precipitate formed was collected and purified by column
chromatography on alumina with acetonitrile–toluene (2 : 1
v/v) as eluent. Yield: 0.146 g, 70% (Found: C, 56.4; H, 3.1; N,
12.0. Calc. for C54H34Cl2N10O8RuؒH2O: C, 56.8; H, 3.0; N,
12.3%). MS [ESMS (CH3OH)]: m/z 1025.1 ([M Ϫ ClO4]ϩ) and
[Ru(tpy)(ptp)][ClO4]2 6. This complex (dark brown) was
synthesized in an identical manner to that described for [Ru-
(tpy)(dppt)][ClO4]2, with 0.227 mmol, 0.087 g ptp in place of
dppt. Yield 0.099 g, 39%. Single crystals suitable for an X-ray
crystallographic study were grown from acetonitrile–toluene
(1 : 1, v/v) at room temperature (Found: C, 52.6; H, 2.7; N, 11.8.
Calc. for C42H26Cl2N8O8RuؒH2O: C, 52.5; H, 2.9; N, 11.7%).
MS [ESMS (CH3OH)]: m/z 843 ([M Ϫ ClO4]ϩ) and 372
1
462.3 ([M Ϫ 2ClO4]2ϩ). H NMR [(CD3)2SO]: δ 9.25 (d, 2H,
J = 7), 9.18 (d, 2H, J = 7), 8.72 (d, 2H, J = 7), 8.66 (d, 2H,
J = 8), 8.48 (d, 2H, J = 7.5), 8.32 (d, 2H, J = 5), 7.62 (dd, 2H),
7.56 (d, 2H, J = 6 Hz), 7.51 (t, 4H), 7.40 (t, 4H), 7.32 (t, 4H),
7.16 (t, 4H) and 6.80 (d, 2H).
1
([M Ϫ 2ClO4]2ϩ). H NMR [(CD3)2SO]: δ 9.50 (d, 1H, J = 9),
9.42 (d, 1H, J = 8), 9.22 (d, 1H, J = 8), 9.17 (d, 2H, J = 8), 8.83
(d, 2H, J = 8), 8.74 (m, 5H), 8.54 (d, 1H, J = 9), 8.38 (d, 1H,
J = 5), 8.18 (d, 1H, J = 8), 7.99 (m, 3H), 7.93 (t, 1H), 7.90
(t, 1H), 7.72 (t, 1H), 7.70 (d, 1H, J = 6), 7.39 (d, 2H, J = 6 Hz)
and 7.13 (t, 2H).
CAUTION: perchlorate salts of metal complexes with
organic ligands are potentially explosive, and only small
amounts of the material should be prepared and handled with
great care.
[Ru(pta)2][ClO4]2 2. This complex was synthesized in an
identical manner to that described for [Ru(dppt)2][ClO4]2, with
0.367 mmol, 0.141 g pta in place of dppt. Yield 0.094 g, 48%
(Found: C, 54.3; H, 2.6; N, 12.5. Calc. for C50H28Cl2N10-
O8Ruؒ2H2O: C, 54.4; H, 2.7; N, 12.7%). MS [ESMS (CH3OH)]:
m/z 967.1 ([M Ϫ ClO4]ϩ) and 434.2 ([M Ϫ 2ClO4]2ϩ). 1H NMR
[(CD3)2SO]: δ 9.37 (d, 2H, J = 7), 9.30 (d, 2H, J = 7), 8.75 (d,
2H, J = 7.5), 8.72 (d, 2H, J = 6.5), 8.67 (d, 2H, J = 6), 8.52
(d, 2H, J = 7.5), 8.44 (d, 2H, J = 6.5), 8.34 (d, 2H, J = 6.5), 8.26
(d, 2H, J = 4 Hz), 8.03 (t, 2H), 7.86 (t, 2H), 7.80 (t, 2H) and 7.61
(dd, 2H).
Physical measurements
The analyses (C, H and N) were performed using a Perkin-
Elmer 240Q elemental analyser. Absorption spectra were
recorded on a Shimadzu MPS-2000 spectrophotometer, 1H
NMR spectra on Varian INOVA-500 and Bruker AMX-600
spectrometers with (CD3)2SO as solvent at room temperature
and SiMe4 as an internal standard and fast atom bombardment
(FAB) mass spectra on a VG ZAB-HS spectrometer in a
3-nitrobenzyl alcohol matrix. Electrospray (ES) mass spectra
were recorded on a LCQ system (Finngan MAT, USA) using
methanol as mobile phase. The spray voltage, tube lens offset,
capillary voltage and capillary temperature were set at 4.50 kV,
30.00 V, 23.00 V and 200 ЊC, respectively, and the quoted m/z
values are for the major peaks in the isotope distribution.
Cyclic voltammetry was performed on an EG&G PAR 273
polarographic analyser and 270 universal programmer. The
supporting electrolyte was 0.1 mol dmϪ3 tetrabutylammonium
perchlorate in acetonitrile freshly distilled from phosphorus
pentaoxide and deaerated by purging with nitrogen. A standard
three-electrode system was used comprising a platinum micro-
cylinder working electrode, platinum-wire auxiliary electrode
and a saturated calomel reference electrode (SCE).
[Ru(ptp)2][ClO4]2 3. This complex was synthesized in an
identical manner to that described for [Ru(dppt)2][ClO4]2, with
0.367 mmol, 0.15 g ptp in place of dppt. Yield 0.108 g, 52%
(Found: C, 56.7; H, 3.0; N, 12.1. Calc. for C54H30Cl2N10O8Ruؒ
H2O: C, 57.0; H, 2.8; N, 12.3%). MS [ESMS (CH3OH)]: m/z
1018.9 ([M Ϫ ClO4]ϩ) and 460.4 ([M Ϫ 2ClO4]2ϩ). 1H NMR
[(CD3)2SO]: δ 9.60 (d, 2H, J = 8), 9.41 (d, 2H, J = 5.5), 9.40 (d,
2H, J = 3.5), 8.80 (d, 2H, J = 3.5), 8.76 (d, 2H, J = 8.5), 8.74 (d,
2H, J = 8), 8.69 (d, 2H, J = 8), 8.57 (d, 2H, J = 8.5), 8.47 (d, 2H,
J = 5), 7.98 (t, 2H), 7.90 (t, 2H), 7.82 (t, 2H), 7.66 (d, 2H, J = 6.5
Hz), 7.65 (t, 2H) and 7.56 (t, 2H).
[Ru(tpy)(dppt)][ClO4]2 4. A mixture of Ru(tpy)Cl3 (0.1 g,
0.227 mmol), dppt (0.093 g, 0.227 mmol) and triethylamine
(1 cm3) in ethanol–water (1 : 1 v/v, 50 cm3) was refluxed for
10 h, during which time the solution turned dark purple. After
being cooled to room temperature, a dark red precipitate was
obtained by addition of aqueous NaClO4 solution. The product
was purified by column chromatography on alumina with
acetonitrile–toluene (1 : 1 v/v) as eluent. Yield: 0.096 g, 45%.
Single crystals suitable for an X-ray crystallographic study were
grown from acetonitrile–toluene (1 : 1, v/v) at room temper-
ature (Found: C, 53.6; H, 2.7; N, 12.3. Calc. for C42H28Cl2-
N8O8Ru: C, 53.4; H, 3.0; N, 11.9%). MS [ESMS (CH3OH)]:
m/z 844 ([M Ϫ ClO4]ϩ) and 373 ([M Ϫ 2ClO4]2ϩ). 1H NMR
[(CD3)2SO]: δ 9.22 (d, 1H, J = 8.5), 9.13 (d, 1H, J = 9), 9.05 (d,
1H, J = 8), 8.78 (d, 2H, J = 8), 8.74 (d, 1H, J = 8.5), 8.67 (d, 1H,
X-Ray crystallography
A summary of pertinent crystallographic data and experi-
mental details for 4, 5 and 6 is shown in Table 1. Diffraction
intensities for complexes 4 and 6 were collected on a Siemens
R3m diffractometer using the ω-scan technique. Lorentz-
polarization and absorption corrections were applied.16 Diffrac-
tion intensities for 5 were collected (hemisphere technique) on a
Bruker SMART Platform CCD diffractometer and an absorp-
J. Chem. Soc., Dalton Trans., 2001, 1326–1331
1327