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M. Hanif et al. / Inorganica Chimica Acta 380 (2012) 211–215
2.1.1. [Chlorido(3,5,6-bicyclophosphite-1,2-O-isopropylidene-
a-D-
glucofuranoside)(
g
6-p-cymene)(triphenylphosphine)ruthenium(II)]
hexafluorophosphate 5
A solution of [RuII( 6-p-cymene)(PPh3)(CH3CN)Cl]PF6 (144 mg,
g
0.2 mmol) and 3,5,6-bicyclophosphite-1,2-O-isopropylidene-a-D-
glucofuranoside (50 mg, 0.2 mmol) in CH2Cl2 (15 mL) was stirred
for 2 h at room temperature. The solvent was reduced to about
3–5 mL and the product was precipitated by addition of pentane
(20–25 mL). The orange yellow powder was filtered, washed with
pentane (2ꢀ 5 mL) and dried under vacuum.
Yield: 176 mg (95%), m.p. 177–178 °C (decomp.). Elemental
analysis, Anal. Calc. for C37H42O6P3F6ClRu: C, 47.98; H, 4.57. Found:
C, 47.69; H, 4.36%. MS (ESI+): m/z 781.4 [MꢁPF6]+.
1H NMR (500.10 MHz, CDCl3, 25 °C): d = 7.64–7.45 (m, 30H, Ha,-
Ar), 6.18 (d, J = 6.3 Hz, 1H, HbAr), 6.13 (d, J = 6.0 Hz, 1H, HbAr), 6.09
b
(d, J = 6.0 Hz, 1H, HaAr), 6.06 (d, J = 6.5 Hz, 1H, HaAr), 5.97 (tr,
J = 3.8 Hz, 2H, Ha,b-1), 5.80 (d, J = 6.3 Hz, 2H, Ha,bAr), 5.45 (d,
J = 6.3 Hz, 1H, HbAr), 5.28 (d, J = 6.3 Hz, 1H, HaAr), 4.98–4.89 (m,
2H, Ha,b-5), 4.58 (d, J = 3.5 Hz, 1H, Hb-2), 4.49 (d, J = 2.2 Hz, 1H,
Ha-3), 4.43 (d, J = 1.9 Hz, 1H, Hb-3), 4.42 (d, J = 3.5 Hz, 1H, Ha-2),
4.24 (tr, J = 9.8 Hz, 1H, Ha-6), 4.20–4.14 (m, 3H, Ha,b-4, Hb-6), 3.71
(m, 1H, Ha-60), 3.40 (m, 1H, Hb-60), 2.81 (m, 1H, CHa), 2.73 (m,
1H, CHb), 1.94 (s, 3H, CH3b), 1.86 (s, 3H, CH3a), 1.46 (s, 6H, CH3a,b),
1.33 (s, 6H, CH3a,b), 1.27–1.25 (m, 12H, CH3a,b) ppm. 31P{1H} NMR
(202.44 MHz, CDCl3, 25 °C): d = 144.7 (d, J = 87 Hz, sugar–Pb),
144.4 (d, J = 89 Hz, sugar–Pa), 32.7 (d, J = 89 Hz, PPh3b), 32.5 (d,
J = 89 Hz, PPh3a), ꢁ144.3 (septet, PF6) ppm.
Fig. 1. Chemical structures of biologically active Ru complexes with N- and P-donor
ligands.
compounds with the general formulae [RuII(
g
6-arene)Cl2(L)],
[RuII( 6-arene)Cl(L)2]X, [RuII( 6-arene)(L)3]X2
g
and
g
( -
g6
arene = benzene, p-cymene; L = imidazole, benzimidazole, N-meth-
ylimidazole, N-butylimidazole, N-vinylimidazole, N-benzoylimi-
dazole; X = Cl, BF4, BPh4) did not exhibit significant in vitro
anticancer activity [41], some derivatives with modified anthra-
cene-based multidrug resistance (MDR) modulators were efficient
Pgp inhibitors and active in anticancer screening assays [42].
In this paper, we present the preparation of a series of RuII(arene)
The diastereomer 5a crystallized at 4 °C from saturated chloro-
form solution within 72 h. The yellow crystals were filtered,
washed with diethylether and dried under vacuum.
1H NMR (400.13 MHz, CDCl3, 25 °C): d = 7.68–7.46 (m, 15H, HAr),
6.07 (m, 2H, HAr), 6.00 (d, J = 3.4 Hz, 1H, H-1), 5.95 (d, J = 6.0 Hz, 1H,
HAr), 5.46 (d, J = 6.0 Hz, 1H, HAr), 4.94 (m, 1H, H-5), 4.51 (s, 1H, H-3),
4.43 (d, J = 3.4 Hz, 1H, H-2), 4.23 (tr, J = 9.8 Hz, 1H, H-6), 4.16 (d,
J = 2.0 Hz,1H, H-4), 3.80 (m, 1H, H-60), 2.86 (m, 1H, CH), 1.82 (s, 3H,
CH3), 1.46 (s, 3H, CH3), 1.34 (s, 3H, CH3), 1.30–1.24 (m, 6 H,
CH3) ppm. 31P{1H} NMR (161.98 MHz, CDCl3, 25 °C): d = 144.7
(d, J = 88 Hz, sugar–P), 32.9 (d, J = 88 Hz, PPh3), ꢁ144.2 (septet, PF6)
ppm.
complexes of the general formula [RuII( 6-p-cymene)(PPh3)
g
(L)Cl]PF6 with carbohydrate-derived phosphites, imidazole or inda-
zole co-ligands with potential biological activity.
2. Experimental
2.1.2. [Chlorido(3,5,6-bicyclophosphite-1,2-O-cyclohexylidene-
a-D-
2.1. Materials
glucofuranoside)(
g
6-p-cymene)(triphenylphosphine)ruthenium(II)]
hexafluorophosphate 6
All reactions were carried out in dry solvents under an inert
atmosphere. All chemicals were obtained from commercial suppli-
ers in analytical grade and used as received. The Ru complexes
A solution of [RuII( 6-p-cymene)(PPh3)(CH3CN)Cl]PF6 (144 mg,
g
0.2 mmol) and 3,5,6-bicyclophosphite-1,2-O-cyclohexylidene-a-D-
glucofuranoside (58 mg, 0.2 mmol) in CH2Cl2 (15 mL) was stirred
for 2 h at room temperature. The solvent was reduced to about
3–5 mL and the product was precipitated by addition of pentane
(20–25 mL). The orange yellow powder was filtered, washed with
pentane (2ꢀ 5 mL) and dried under vacuum.
bis[dichlorido(
p-cymene)(triphenylphosphine)ruthenium(II)]
do(3,5,6-bicyclophosphite-1,2-O-isopropylidene-
side)(
6-p-cymene)ruthenium(II)] 3, [dichlorido(3,5,6-bicyclop-
hosphite-1,2-O-cyclohexylidene- -glucofuranoside)(
6-p-cym-
ene) ruthenium(II)] 4 [34] and [RuII( 6-p-cymene)(PPh3) (CH3CN)
Cl]PF6 7 [44], and the ligands 3,5,6-bicyclophosphite-1,2-O-isopro-
pylidene- -glucofuranoside I and 3,5,6-bicyclophosphite-1,2-O-
g -
6-p-cymene)ruthenium(II)] 1 [43], [dichlorido(g6
2
[24], [dichlori-
a
-D-glucofurano-
g
a
-
D
g
Yield: 185 mg (96%), m.p. 178–180 °C (decomp.). Elemental
analysis, Anal. Calc. for C40H46O6P3F6ClRu: C, 49.72; H, 4.80. Found:
C, 49.44; H, 4.53%. MS (ESI+): m/z 821.5 [MꢁPF6]+.
g
a
-D
1H NMR (500.10 MHz, CDCl3, 25 °C): d = 7.64–7.45 (m, 30H, Ha,-
b
cyclohexylidene-
a
-
D
-glucofuranoside II [45] were synthesized
Ar), 6.17 (d, J = 6.0 Hz, 1H, HaAr), 6.10 (m, 2H, Ha,bAr), 6.00 (d,
according to literature procedures. 1H, 13C{1H} and 31P{1H} NMR
J = 6.3 Hz, 1H, HbAr), 5.96 (tr, J = 3.8 Hz, 2H, Ha,b-1), 5.79 (m, 2H, Ha,-
b
spectra were recorded at 25 °C on a Bruker FT NMR spectrometer
Ar), 5.46 (d, J = 6.6 Hz, 1H, HaAr), 5.31 (d, J = 6.3 Hz, 1H, HbAr), 4.97–
Avance III 500 MHz at 500.10 (1H), 125.75
(
13C{1H}) and
4.87 (m, 2H, Ha,b-5), 4.55 (d, J = 3.5 Hz, 1H, Ha-2), 4.50 (d, J = 2.5 Hz,
1H, Hb-3), 4.45 (d, J = 2.2 Hz, 1H, Ha-3), 4.39 (d, J = 3.9 Hz, 1H, Hb-
2), 4.24 (tr, J = 9.8 Hz, 1H, Hb-6), 4.20–4.13 (m, 3H, Ha,b-4, Ha-6),
3.71 (m, 1H, Hb-60), 3.42 (m, 1H, Ha-60), 2.79 (m, 1H, CHb), 2.71
202.44 MHz (31P{1H}) or on a Bruker DPX 400 MHz at 400.13 (1H),
100.63 (13C{1H}) and 161.98 MHz (31P{1H}) and the 2D NMR spectra
were collected in a gradient-enhanced mode. Melting points were
measured on a Büchi B-540 apparatus and are uncorrected. Elemen-
tal analysis was determined by the Laboratory for Elemental Anal-
ysis, Faculty of Chemistry, University of Vienna, on a Perkin-Elmer
2400 CHN Elemental Analyzer. Electrospray ionization mass spec-
(m, 1H, CHa), 1.92 (s, 3H, CH3a), 1.84 (s, 3H, CH3b), 1.69–1.49 (m,
a,b
16H, CH2a,b), 1.43–1.35 (m, 4H, CH2a,b), 1.25–1.20 (m, 12H, CH3
)
ppm. 31P{1H} NMR (202.44 MHz, CDCl3, 25 °C): d = 144.6 (d,
J = 87 Hz, sugar–P), 144.5 (d, J = 87 Hz, sugar–P), 32.3 (d,
J = 89 Hz, PPh3), 32.4 (d, J = 87 Hz, PPh3), ꢁ144.3 (septet, PF6) ppm.
tra were recorded on a Bruker esquire3000
.