10.1002/ejic.201601226
European Journal of Inorganic Chemistry
FULL PAPER
-
2+
2NO3
]
m/z 509.03, found m/z 509.08. Elemental analysis (%): Calcd for
Synthesis of [Ru2(η6-p-cymene)2(p-bib)2Cl2](NO3)2 (10)
Ru2C48H56N10Cl2O6•CH2Cl2•H2O C 47.27, H 4.86, N 11.25; found: C 46.82, H 4.81, N 11.16.
To a solution of [Ru2(η6-p-cymene)2(p-bib)2Cl2](Cl)2 (21.76 mg, 0.02 mmol) in MeOH (5 mL),
Synthesis of [Ru2(η6-p-cymene)2(m-bib)2Br2](Br)2 (5)
a solution of AgNO3 (6.79 mg, 0.04 mmol) in MeOH (5 mL) was added. The mixture was
stirred at room temperature for
2 h, and then the solvent was removed on a rotary
A solution of [Ru2(η6-p-cymene)2(m-bib)2Cl2](Cl)2 (43.52 mg, 0.04 mmol) in MeOH (5 mL)
was stirred at room temperature for 30 min. A solution of KBr (50 equiv, 238 mg) in MeOH
(15 mL) was added dropwise to the mixture and stirred for another 24 h. The solvent was
removed under reduced pressure. The residue was subsequently purified by silica gel
chromatography to give yellow solid (21.8 mg, yield 43.0%). 1H NMR (DMSO, 400 MHz) δ:
8.64 (2H, s, Him), 8.19 (2H, s, Him), 7.51 (2H, s, Him), 7.18 (8H, m, Hbz, m-bib), 7.09 (4H, d,
Him), 6.93 (2H, m, Hbz, m-bib), 6.03 (4H, d, Hbz, p-cymene), 5.78 (4H, d, Hbz, p-cymene),
5.20 (8H, d, CH2), 2.66 (2H, m, CH), 1.74 (6H, s, CH3), 1.11 (12H, d, CH3). ESI-MS(+):
calcd for [5-2Br-]2+ m/z 553.49, found m/z 553.33. Elemental analysis (%): Calcd for
Ru2C48H56N8Br4•3H2O C 43.65, H 4.73, N 8.48; found C 43.76, H 4.95, N 8.44.
evaporator. The residue was purified by flash column chromatography with CH2Cl2/CH3OH
as elution mixture to afford yellow solid (10.6 mg, yield 46.4%). 1H NMR (CDCl3, 400 MHz)
δ: 8.83 (4H, d, Him), 7.34 (4H, d, Him), 6.98 (8H, d, Hbz, p-bib), 6.68 (4H, d, Him), 5.76 (4H, d,
Hbz, p-cymene), 5.64 (4H, d, Hbz, p-cymene), 5.48 (4H, d, CH2), 4.90 (4H, d, CH2) 2.47 (2H,
-
2+
m, CH), 1.81 (6H, s, CH3), 1.16 (12H, m, CH3). ESI-MS(+): calcd for [10-2NO3
]
m/z
510.25, found m/z 509.03. Elemental analysis (%): Calcd for Ru2C48H56N10Cl2O6•CH2Cl2
C
47.97, H 4.76, N 11.42; found C 47.78, H 4.90, N 11.78.
Synthesis of [Ru2(η6-p-cymene)2(p-bib)2Br2](Br)2 (11)
A solution of [Ru2(η6-p-cymene)2(p-bib)2Cl2](Cl)2 (43.52 mg, 0.04 mmol) in MeOH (5 mL)
was stirred at room temperature for 30 min, a solution of KBr (50 equiv, 238 mg) in MeOH
(15 mL) was added dropwise, and the mixture was stirred for another 24 h. The solvent was
removed under reduced pressure. The residue was purified by flash column
chromatography to give yellow solid (21.6 mg, 42.7%). 1H NMR (DMSO, 400 MHz) δ: 8.03
(4H, d, Him), 7.34 (4H, d, Him), 7.14 (4H, d, Him), 7.06 (8H, d, Hbz, p-bib), 5.96 (4H, d, Hbz, p-
cymene), 5.71 (4H, d, Hbz, p-cymene), 5.22 (8H, d, CH2), 2.64 (2H, m, CH), 1.80 (6H, s,
CH3), 1.11 (12H, m, CH3). ESI-MS(+): calcd for [11-2Br-]2+ m/z 553.49, found m/z 553.75.
Elemental analysis (%): Calcd for Ru2C48H56N8Br4•3H2O C 43.65, H 4.73, N 8.48; found C
43.55, H 4.74, N 8.35.
Synthesis of [Ru2(η6-p-cymene)2(m-bib)2I2](I)2 (6)
A solution of [Ru2(η6-p-cymene)2(m-bib)2Cl2](Cl)2 (43.52 mg, 0.04 mmol) in MeOH (5 mL)
was stirred at room temperature for 30 min. A solution of KI (50 equiv, 332 mg) in MeOH
(15 mL) was added dropwise to the mixture and stirred for another 24 h. The solvent was
removed under reduced pressure. The residue was recrystallized with CHCl3 to give yellow
crystals (23.1 mg, yield 39.6%). 1H NMR (DMSO, 400 MHz) δ: 8.26 (2H, s, Him), 8.19 (2H, s,
Him), 7.51 (2H, s, Him), 7.18 (8H, m, Hbz, m-bib), 7.09 (4H, d, Him), 6.93 (2H, m, Hbz, m-bib),
6.03 (4H, d, Hbz, p-cymene), 5.78 (4H, d, Hbz, p-cymene), 5.20 (8H, d, CH2), 2.66 (2H, m,
CH), 1.74 (6H, s, CH3), 1.11 (12H, d, CH3). ESI-MS(+): calcd for [6-2I-]2+ m/z 600.48, found
m/z 601.17. Elemental analysis (%): Calcd for Ru2C48H56N8I4•2H2O C 38.67, H 4.06, N 7.52;
found C 38.78, H 4.30, N 7.37.
Synthesis of [Ru2(η6-p-cymene)2(p-bib)2I2](I)2 (12)
A solution of [Ru2(η6-p-cymene)2(p-bib)2Cl2](Cl)2 (43.52 mg, 0.04 mmol) in MeOH (5 mL)
was stirred at room temperature for 30 min, a solution of KI (50 equiv, 332 mg) in MeOH
(15 mL) was added dropwise, and the mixture was stirred for another 24 h. The solvent was
removed under reduced pressure. The residue was purified by flash column
chromatography to give yellow solid (23.4 mg, 40.2%). 1H NMR (DMSO, 400 MHz) δ: 8.03
(4H, d, Him), 7.32 (4H, d, Him), 7.18 (4H, d, Him), 7.08 (8H, d, Hbz, p-bib), 6.09 (4H, d, Hbz, p-
cymene), 5.75 (4H, d, Hbz, p-cymene), 5.20 (8H, d, CH2), 2.71 (2H, m, CH), 1.72 (6H, s,
CH3), 1.12 (12H, m, CH3). ESI-MS(+): calcd for [12-2I-]2+ m/z 600.48, found m/z 601.25.
Elemental analysis (%): Calcd for Ru2C48H56N8I4•2H2O C 38.67, H 4.06, N 7.52; found C
38.67, H 4.32, N 7.34.
Synthesis of [Ru2(η6-p-cymene)2(p-bib)2Cl2](Cl)2 (7)
To a solution of [RuCl2(η6-p-cymene)]2 (61.2 mg, 0.1 mmol) in MeOH (15 mL), the ligand p-
bib (47.8 mg, 0.2 mmol) was added. The reaction mixture was stirred at 338 K for 6 h, the
solvent was then removed under reduced pressure. The residue was subsequently purified
by silica gel chromatography to give yellow solid (45.7 mg, yield 41.9%). 1H NMR (CDCl3,
400 MHz) δ: 9.74 (4H, d, Him), 7.39 (4H, d, Him), 7.06 (8H, d, Hbz, p-bib), 6.58 (4H, s, Him),
5.82 (8H, d, Hbz, p-cymene), 5.69 (4H, d, CH2), 4.89 (4H, d, CH2) 2.44 (2H, m, CH), 1.85
(6H, s, CH3), 1.17 (12H, m, CH3). ESI-MS(+): calcd for [7-2Cl]2+ m/z 509.03, found m/z
509.33; calcd for [7-Cl]+ m/z 1053.52, found m/z 1053.75. Elemental analysis (%): Calcd for
Ru2C48H56N8Cl4•CH2Cl2•2H2O C 49.38, H 5.07, N 9.40; found C 48.94, H 5.37, N 9.36.
Determination of X-ray Crystal Structure
Synthesis of [Ru2(η6-p-cymene)2(p-bib)2Cl2](CF3SO3)2 (8)
Single-crystal X-ray diffraction data were measured at 296(2) K for complexes 2, 3, 6 and at
298 K for complex 8 on a Bruker Apex II CCD using Mo Kα radiation (λ= 0.71073 Å). An
empirical absorption correction was applied to the data by using the SADABS program. The
structures were solved by direct methods and refined by full-matrix least-squares methods
with SHELX.[32] All non-hydrogen atoms were refined anisotropically and hydrogen atoms of
organic molecule were placed in calculated positions, assigned isotropic thermal
parameters, and allowed to ride their parent atoms. The following computer programs and
hardware were used: structure solution, SHELXS-2014/7; structure refinement, SHELXL-
2014/7. Data collection parameters and structure refinement details are given in Table S1 in
the supporting information. CCDC 1502211 (for 2), 1502212 (for 3), 1502213 (for 6),
1502214 (for 8) containing the supplementary crystallographic data for this paper that can
be obtained free of charge from The Cambridge Crystallographic Data Centre.
To a solution of [RuCl2(η6-p-cymene]2 (61.2 mg, 0.1 mmol) in CH2Cl2 (15 mL), a solution of
AgCF3SO3 (51.38 mg, 0.2 mmol) in EtOAc (5 mL) was added. The resulting mixture was
stirred at room temperature for 2 h, the AgCl precipitate was then removed by filtration. The
ligand p-bib (47.8 mg, 0.2 mmol) was added to the resulting solution. The mixture was
stirred at RT for another 6 h, and then the solvent was removed on a rotary evaporator. The
residue was recrystallized from CHCl3 to give yellow crystals (43.0 mg, yield 32.6%). 1H
NMR (CDCl3, 400 MHz) δ: 8.63 (4H, d, Him), 7.37 (4H, d, Him), 7.04 (8H, d, Hbz, p-bib), 6.71
(4H, s, Him), 5.77 (4H, d, Hbz, p-cymene), 5.65 (4H, d, CH2), 5.54 (4H, d, CH2), 4.94 (4H, d,
CH2), 2.49 (2H, m, CH), 1.84 (6H, s, CH3), 1.13 (12H, m, CH3). ESI-MS(+): calcd for [8-
-
2+
- +
2CF3SO3
]
m/z 509.03, found m/z 509.33; calcd for [8-CF3SO3 ] m/z 1167.14, found m/z
1166.00. Elemental analysis (%): Calcd for Ru2C50H56N8Cl2F6S2O6 C 45.63; H 4.29, N 8.51;
found C 45.23, H 4.26, N 8.24.
Gel Electrophoresis Experiments
[Ru2(η6-p-cymene)2(p-bib)2Cl2](SbF6)2 (9)
The closed circular supercoiled pBR322 plasmid DNA was used for the gel electrophoresis
experiments, which was purchased from Sangon Biotech (Shanghai, China). DNA (1 µL, 10
µM) was treated with 4 µL ultrapure water, 5 µL PBS buffer (100 mM) and 10 µL different
concentrations of complexes (molar ratio of [M]/[DNA] ri = 1, 2, 3, 4, 5, 6). The mixture was
incubated at 310 K for 12 h in the dark, then 4 µL loading buffer (0.05% Bromophenol Blue,
30 mM EDTA, 36% glycerol, 0.05% Xylene Cyanol FF) was added. Electrophoresis was
carried out in a native agarose gel (1%) in 1×TAE buffer for 2 h at 70 mA. The gel was
To a solution of [Ru2(η6-p-cymene)2(p-bib)2Cl2](Cl)2 (21.76 mg, 0.02 mmol) in MeOH (5 mL),
a solution of AgSbF6 (13.74 mg, 0.04 mmol) in MeOH (5 mL) was added. The mixture was
stirred at room temperature for
evaporator. The residue was recrystallized from CHCl3 to give yellow solid (12.1 mg, yield
40.6%). 1H NMR (CDCl3, 400 MHz) δ: 7.97 (4H, d, Him), 7.30 (4H, d, Him), 6.95 (8H, d, Hbz
2 h, and then the solvent was removed on a rotary
,
subsequently stained with
1 µg/mL ethidium bromide and visualized under a UV
p-bib), 6.84 (4H, s, Him), 5.74 (4H, d, Hbz, p-cymene), 5.54 (4H, d, Hbz, p-cymene), 5.31 (4H,
transilluminator and photographed using a digital camera.
d, CH2), 4.97 (4H, d, CH2), 2.57 (2H, m, CH), 1.86 (6H, s, CH3), 1.19 (12H, m, CH3). ESI-
-
2+
MS(+): calcd for [9-2SbF6
]
m/z 509.03, found m/z 509.25. Elemental analysis (%): Calcd
for Ru2C48H56N8Cl2Sb2F12 C 38.70, H 3.79, N 7.52; found: C 38.45, H 3.67, N 7.42.
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