◦
(2C, +, Mepyr), 40.5 (2 C, +, MeN), 111.6 (2 C, +, ArH, C-3ꢀ),
122.9 (2 C, +, ArH, C-2ꢀ), 133.8 (1 C, 0, Ar, C-4 pyr), 139.1 (2 C, 0,
Ar, C-3 pyr/C-5 pyr), 143.7 (1 C, 0, Ar, C-1ꢀ), 151.2 (1 C, 0, Ar, C-4ꢀ).
135◦, HETCOR) dC/ppm (500 MHz, DMSO-d6, 25 C, Me4Si):
11.1 (+, Me-5pyr), 12.1 (+, Me-3pyr), 111.1 (+, ArH, C-4ꢀ), 122.6
(+, ArH, C-8ꢀ), 124.3 (+, ArH, C-5ꢀ), 124.7 (+, ArH, C-7ꢀ), 126.4
(+, ArH, C-3ꢀ), 129.6 (0, Ar, C-8aꢀ), 130.0 (+, ArH, C-2ꢀ), 133.3
(0, Ar, C-4aꢀ), 135.3 (0, Ar, C-4pyr), 138.2 (+, ArH, C-4bpy), 140.5
(0, Ar, C-3), 141.1 (0, Ar, C-5), 142.0 (+, ArH, C-3bpy), 143.0 (+,
ArH, C-5bpy), 145.7 (0, Ar, C-6ꢀ), 146.1 (0, Ar, C-1ꢀ), 150.0 (0, Ar,
C-2bpy), 152.4 (+, ArH, C-6bpy).
(NH4)2[(H2O)3ClRu(l-dmpzn)2RuCl(H2O)3] (3). An excess of
ligand 1 (0.166 g, 0.48 mmol) was added to a solution of RuCl3
(0.050 g, 0.24 mmol) in methanol (50 cm3). The mixture was stirred
at 50 ◦C for 12 h under N2 in the dark and the solvent was removed
under reduced pressure. Recrystallization from cold methanol gave
3 as a crystalline brown solid obtained as the ammonium salt,
which was filtered off, washed with alcohol and diethyl ether, and
vacuum dried. Yield of 3: 0.22 g, 85%. Found: C, 33.42; H, 4.12;
N, 13.10%. Calc. for C30H44Cl2N10O12Ru2S2: C, 33.55; H, 4.10;
(NH4)2[(H2O)(NO)Cl2Ru(l-dmpzn)2RuCl2(NO)(H2O)]
(6).
This complex was prepared in a similar way to 3 but using ligand
1 (0.146 g, 0.42 mmol) and RuCl3NO (0.050 g, 0.21 mmol). A
reddish brown crystalline solid was obtained as ammonium salt.
Yield of 6: 0.215 g, 90%. Found: C, 31.77; H, 3.20; N, 14.90%.
Calc. for C30H36Cl4N12O10Ru2S2: C, 31.80; H, 3.18; N, 14.84%. IR
N, 13.05%. IR mmax/cm−1 (KBr): 3500/3440s (NH4 ), 3200 (OH2),
+
as
1634w (C C), 1584m (C N), 1457W (N N), 1198s ( SO3−), 1031s
=
=
=
(sSO3−). 1H NMR dH/ppm (500 MHz, DMSO-d6, 25 ◦C, Me4Si):
mmax/cm−1 (KBr): 3520/3400s (NH4 ), 3300 (OH2), 1876s (NO),
+
2.60 (6 H, s, Mepyr), 7.18 (4 H, t, J1 = 50 Hz, 14NH4 ), 7.64 (1 H,
1634w (C C), 1583m (C N), 1450w (N N), 1181S ( SO3−), 1033s
+
as
=
=
=
dd, J3 = 10 Hz, J3 = 10 Hz, H-3ꢀ), 7.71 (1 H, d, J3 = 10 Hz, H-4ꢀ),
7.86 (1 H, d, J3 = 9.8 Hz, H-7ꢀ), 8.08 (1 H, d, J3 = 10 Hz, H-2ꢀ),
8.26 (1 H, s, H-5ꢀ), 8.66 (1 H, d, J3 = 9.7 Hz, H-8ꢀ). 13C NMR
(NOE suppression, DEPT-135◦, HETCOR) dC/ppm (500 MHz,
DMSO-d6, 25 ◦C, Me4Si): 12.1 (2 C, +, Me), 111.1 (1 C, +, ArH,
C-4ꢀ), 122.6 (1 C, +, ArH, C-8ꢀ), 124.3 (1 C, +, ArH, C-5ꢀ), 124.7
(1 C, +, ArH, C-7ꢀ), 126.4 (1 C, +, ArH, C-3ꢀ), 129.6 (1 C, 0, Ar,
C-8aꢀ), 130.0 (1 C, +, ArH, C-2ꢀ), 133.3 (1 C, 0, Ar, C-4aꢀ), 135.3
(1 C, 0, Ar, C-4pyr), 140.4 (2 C, 0, Ar, C-3pyr/C-5pyr), 145.7 (1 C, 0,
Ar, C-6ꢀ), 147.7 (1 C, 0, Ar, C-1ꢀ).
(sSO3−). 1H NMR dH/ppm (500 MHz, DMSO-d6, 25 ◦C, Me4Si):
2.65 (6H, s, Me), 7.09 (4H, t, J1 = 50 Hz, 14NH4 ), 7.24 (1 H, s,
+
H-5ꢀ), 7.61 (1H, dd, J3 = 10 Hz, J3 = 10 Hz, H-3ꢀ), 7.71 (1 H, d,
J3 = 10 Hz, H-4ꢀ), 7.85 (1 H, d, J3 = 9.8 Hz, H-7ꢀ), 8.06 (1 H, d,
J3 = 10 Hz, H-2ꢀ), 8.63 (1 H, d, J3 = 9.7 Hz, H-8ꢀ). 13C NMR
(NOE suppress◦ion, DEPT-135◦, HETCOR) dC/ppm (500 MHz,
DMSO-d6, 25 C, Me4Si): 12.6 (2 C, +, Mepyr), 111.1 (1 C, +,
ArH, C-4ꢀ), 122.6 (1 C, +, ArH, C-8ꢀ), 124.2 (1 C, +, ArH, C-5ꢀ),
124.7 (1 C, +, ArH, C-7ꢀ), 126.3 (1 C, +, ArH, C-3ꢀ), 129.8 (1 C,
0, Ar, C-8aꢀ), 130.1 (1 C, +, ArH, C-2ꢀ), 133.2 (1 C, 0, Ar, C-4aꢀ),
135.4 (1 C, 0, Ar, C-4pyr), 140.8 (2 C, 0, Ar, C-3pyr/C-5pyr), 145.9
(1 C, 0, Ar, C-6ꢀ), 147.8 (1 C, 0, Ar, C-1ꢀ).
[(H2O)3ClRu(l-dmpza)2RuCl(H2O)3] (4). This complex was
prepared in a similar way to 3 but using ligand 2 (0.117 g,
0.48 mmol). A brown crystalline solid was obtained. Yield of 4:
0.168 g, 80.5%. Found: C, 35.95; H, 5.11; N, 16.23%. Calc. for
C26H44Cl2N10O6Ru2: C, 36.06; H, 5.09; N, 16.18%. IR mmax/cm−1
[(H2O)(NO)Cl2Ru(l-dmpza)2RuCl2(NO)(H2O)]
(7). This
complex was prepared in a similar way to 3 but using ligand
2 (0.102 g, 0.42 mmol) and RuCl3NO (0.050 g, 0.21 mmol).
A reddish brown crystalline solid was obtained. Yield of 7:
0.156 g, 80%. Found: C, 33.62; H, 3.92; N, 18.25%. Calc. for
(KBr): 3300s (OH2), 1603w (C C), 1563m (C N). 1H NMR
dH/ppm (500 MHz, DMSO-d6, 25 ◦C, Me4Si): 2.55 (6 H, s, Me),
3.01 (6 H, s, MeN), 6.78 (2 H, d, J3 = 11 Hz, H-3ꢀ), 7.63 (2 H,
d, J3 = 11 Hz, H-2ꢀ). 13C NMR (NOE suppression, DEPT-135◦,
=
=
C26H36Cl4N12O4Ru2: C, 33.76; H, 3.90; N, 18.18%. IR mmax/cm−1
1
=
=
(KBr): 3300s (OH2), 1870s (NO), 1601m (C N, C C). H NMR
dH/ppm (500 MHz, DMSO-d6, 25 ◦C, Me4Si): 2.55 (6 H, s, Mepyr),
3.05 (6 H, s, Me–N), 6.62 (2 H, d, J3 = 12 Hz, H-3ꢀ), 7.75 (2 H,
d, J3 = 12 Hz, H-2ꢀ). 13C NMR (NOE suppression, DEPT-135◦,
HETCOR) dC/ppm (500 MHz, DMSO-d6, 25 ◦C, Me4Si): 11.9
(2 C, +, Mepyr), 39.9 (2 C, +, Me–N), 111.7 (2 C, +, ArH, C-3ꢀ),
123.0 (2 C, +, ArH, C-2ꢀ), 133.8 (1 C, 0, Ar, C-4pyr), 139.2 (2 C,0,
Ar, C-3pyr/C-5pyr), 143.7 (1 C, 0, Ar, C-1ꢀ), 151.3 (1 C, 0,Ar, C-4ꢀ).
◦
HETCOR) dC/ppm (500 MHz, DMSO-d6, 25 C,; Me4Si): 11.9
(2 C, +, Mepyr), 39.9 (2 C, +, MeN), 111.7 (2 C, +, ArH, C-3ꢀ),
122.9 (2 C, +, ArH, C-2ꢀ), 133.8 (1 C, 0, Ar, C-4pyr), 137.2 (2 C, 0,
Ar, C-3pyr/C-5pyr), 143.7 (1 C, 0, Ar, C-1ꢀ), 152.2 (1 C, 0, Ar, C-4ꢀ).
cis-[Ru(dmpzn)(bpy)2Cl] (5). cis-[Ru(bpy)2Cl2] (prepared as
previously reported24) (0.500 g, 1 mmol) was dissolved in DMF
(10 cm3) and ligand 1 (0.360 g, 1 mmol) was added. The mixture
was stirred at 70 ◦C for 8 h in dark. The reaction mixture was
allowed to cool room to temperature and the fine precipitate of
ammonium chloride was filtered off. The filtrate was then added
dropwise over cold diethyl ether and cooled at 4 ◦C for 8 h.
The solid was filtered off and the reddish brown crystalline solid
was collected by filtration and washed with cold water, ethanol
and ether and vacuum dried. Yield of 5: 0.600 g, 77%. Found:
C, 53.82; H, 3.71; N, 14.45%. Calc. for C35H29ClN8O3RuS: C,
cis-[Ru(NO)(dmpzn)(bpy)2]Cl2 (8). A solution of 5 (0.300 g)
and LiCl (0.5 g) in methanol (35 mL) was bubbled with NO
for 20 min under nitrogen. After stirring for 3 h the solvent was
removed under reduced pressure. The obtained solid was washed
with cold water to remove the excess of LiCl, filtered off and dried
under vacuum to give 8 as a deep red solid. Yield of 8: 0.30 g, 92%.
IR mmax/cm−1 (KBr): 1879s (NO), 1632w (C C), 1586m (C N),
=
=
1455w (N N), 1197s ( SO3−), 1032s (sSO3−). H NMR dH/ppm
(500 MHz, DMSO-d6, 25 ◦C, Me4Si): 2.55 (3 H, s, Me-3pyr), 2.60
(3 H, s, Me-5pyr), 7.70 (1 H, dd, H-3ꢀ), 7.85 (1 H, d, H-4ꢀ), 8.00 (1 H,
d, H-7ꢀ), 8.10 (2 H, m, H-4bpy), 8.20 (1 H, d, H-2ꢀ), 8.30 (1 H, d,
H-5ꢀ), 8.52–8.48 (4 H, m, H-5bpy), 8.54 (1 H, s, H-8ꢀ), 8.95 (4 H, m,
H-3bpy), 9.05 (1 H, d, H-6ꢀꢀbpy), 9.15 (1 H, d, H-6IV (bpy)), 9.50 (2 H, d,
as
1
=
54.01; H, 3.73; N, 14.40%. IR mmax/cm−1 (KBr): 1632w (C C),
=
1586m (C N), 1455w (N N), 41197s ( SO3−), 1032s (sSO3−). H
NMR dH/ppm (500 MHz, DMSO-d6, 25 ◦C, Me4Si): 2.55 (3 H, s,
Me-3pyr), 2.60 (3 H, s, Me-5pyr), 7.62 (1 H, dd, H-3ꢀ), 7.70 (1 H,
d, H-4ꢀ), 7.86 (1 H, d, H-7ꢀ), 8.00 (4 H, d, H-3bpy), 8.30 (1 H, d,
H-2ꢀ), 8.51 (4 H, t, H-4bpy), 8.54 (1 H, s, H-8ꢀ), 8.65 (4 H, t, H-5bpy),
8.86 (4 H, d, H-6bpy), 13.10 (1 H, br s, NH). 13C NMR (DEPT-
as
1
=
=
H-6ꢀꢀꢀbpy), 9.65 (1 H, d, H-6V (bpy trans to NO)), 13.12 (1 H, br s, NH). 13
C
NMR (DEPT-135◦, HETCOR) dC/ppm (500 MHz, DMSO-d6,
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The Royal Society of Chemistry 2008
Dalton Trans., 2008, 3559–3566 | 3565
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