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was then cooled down to –40 °C overnight. The dark red crystalline
product is finally filtered, washed with diethyl ether and dried under
vacuum to yield 3.39 g (96 %) of [Ru(η6-p-cymene)2Cl2]2. 1H NMR
(300 MHz, CDCl3): δ (ppm) 5.47 (d, 2H), 5.33 (d, 2H), 2.92 (hept., 1H),
2.15 (s, 3H), 1.27 (d, 6H).
General Procedure for the Synthesis of [(η6-benzene)Ru-
(N^N)Cl](PF6) (N^N = bpy, phen, phenamine, phendione, TMS-
EPIP)
(s, 2H), 5.78 (s, 2H), 5.48 (s, 2H), 2.65 (hept., 1H), 2.05 (s, 3H), 0.97
(dd, J = 6.9, 3.1 Hz, 6H). ESI-MS: m/z 465.6 [M-PF6]+.
[(η6-p-cymene)Ru(phendione)Cl] (PF6): Yield: 91 %. 1H NMR
(300 MHz, CD3CN): δ (ppm) 9.69 (d, J = 5.3 Hz, 2H), 8.64 (d, J =
7.9 Hz, 2H), 7.98 (dd, J = 7.7, 5.7 Hz, 2H), 6.30 (d, J = 6.4 Hz, 2H),
6.06 (d, J = 6.0 Hz, 2H), 2.61 (hept., 1H), 2.22 (s, 3H), 0.96 (d, J =
6.8 Hz, 6H). ESI-MS: m/z 481.2 [M-PF6]+.
[(η6-p-cymene)Ru(dppz)Cl] (PF6): Yield: 95 %. 1H NMR (300 MHz,
DMSO d6): δ (ppm) 10.01 (d, J = 5.2 Hz, 2H), 9.74 (d, J = 8.1 Hz, 2H),
8.49 (dd, J = 6.3, 3.4 Hz, 2H), 8.31 (dd, J = 8.1, 5.4 Hz, 2H), 8.17 (dd,
A solution of [(η6-benzene)RuCl2]2 (150 mg, 0.3 mmol) and N^N
diimine ligand (0.6 mmol) in methanol (50 mL) was heated to reflux
overnight. Solvent was removed under reduced pressure and the J = 6.4, 3.4 Hz, 2H), 6.39 (d, J = 6.2 Hz, 2H), 6.16 (d, J = 6.2 Hz, 2H),
resulting precipitate dissolved in water (5 mL). Dropwise addition
of a saturated KPF6 aqueous solution gave a dark to bright yellow
solid, which was collected, washed thoroughly with water (5 x
10 mL), diethyl ether (3 x 10 mL) and finally dried under vacuum.
[(η6-benzene)Ru(bpy)Cl](PF6): Yield: 91 %. 1H NMR (300 MHz,
MeOD): δ (ppm) 9.40 (d, J = 5.6 Hz, 2H), 8.31 (d, J = 8.1 Hz, 2H),
8.18 (t, J = 7.8 Hz, 2H), 7.68 (t, J = 6.6 Hz, 2H), 6.01 (s, 6H). ESI-MS:
m/z 371.0 [M-PF6]+.
[(η6-benzene)Ru(phen)Cl](PF6): Yield: 93 %. 1H NMR (300 MHz,
CD3CN): δ (ppm) 9.74 (d, J = 5.2 Hz, 2H), 8.75 (d, J = 8.2 Hz, 2H),
8.14 (s, 2H), 8.02 (dd, J = 8.2, 5.3 Hz, 2H), 6.10 (s, 6H). ESI-MS:
m/z 395.0 [M-PF6]+.
2.79–2.62 (hept., 1H), 2.21 (s, 3H), 1.00 (d, J = 6.8 Hz, 6H). ESI-MS:
m/z 553.3 [M-PF6]+.
General Procedure for the Synthesis of [(η6-arene)Ru-
(N^N)OTf](OTf) (arene = bpy or p-cymene; N^N = bpy, phen,
phenamine)
Trifluoromethanesulfonic acid (500 μL, 5.65 mmol, 100 equiv.) was
carefully added to a suspension of [Ru(η6-arene)(N^N)Cl](PF6)
(150 mg) in dichloromethane (50 mL). The reaction mixture was
stirred at room temperature in the dark overnight. Addition of di-
ethyl ether gave a yellowish precipitate, which was collected,
washed thoroughly with diethyl ether and finally dried under vac-
uum.
[(η6-benzene)Ru(phenamine)Cl](PF6): Yield: 94 %. 1H NMR
(300 MHz, CD3CN): δ (ppm) 9.71 (d, J = 5.3 Hz, 1H), 9.34 (d, J =
5.2 Hz, 1H), 8.73 (d, J = 8.5 Hz, 1H), 8.31 (d, J = 8.3 Hz, 1H), 7.97 (dd,
J = 8.5, 5.3 Hz, 1H), 7.76 (dd, J = 8.3, 5.2 Hz, 1H), 7.05 (s, 1H), 6.05
(s, 6H), 5.48 (s, 2H). ESI-MS: m/z 409.6 [M-PF6]+.
[(η6-benzene)Ru(phendione)Cl](PF6): Yield: 93 %. 1H NMR
(300 MHz, CD3CN): δ (ppm) 9.81 (dd, J = 5.6, 1.2 Hz, 2H), 8.65 (dd,
J = 7.9, 1.2 Hz, 2H), 7.99 (dd, J = 7.9, 5.6 Hz, 2H), 6.31 (s, 6H). ESI-
MS: m/z 425.0 [M-PF6]+.
[(η6-benzene)Ru(bpy)(OTf)](OTf): Yield: 91 %. 1H NMR (300 MHz,
CD3OD): δ (ppm) 9.81 (d, J = 5.5 Hz, 2H), 8.59 (d, J = 8.2 Hz, 2H),
8.39 (t, J = 7.9 Hz, 2H), 7.92 (t, J = 6.6 Hz, 2H), 6.33 (s, 6H). ESI-MS:
m/z 485.1 [M-OTf]+, 168.0 [M-2OTf]2+
.
[(η6-p-cymene)Ru(bpy)(OTf)](OTf): Yield: 94 %. 1H NMR (300 MHz,
CD3OD): δ (ppm) 9.82 (d, J = 5.7 Hz, 2H), 8.63 (d, J = 8.1 Hz, 2H),
8.42 (t, J = 8.0 Hz, 2H), 7.96 (t, J = 6.6 Hz, 2H), 6.45 (d, J = 6.3 Hz,
2H), 6.23 (d, J = 6.3 Hz, 2H), 2.57 (hept., J = 6.8 Hz, 1H), 2.30 (s,
3H), 1.03 (d, J = 6.9 Hz, 6H). ESI-MS: m/z 540.8 [M-OTf]+, 196.2 [M-
2OTf]2+
.
[(η6-benzene)Ru(TMS-EPIP)Cl](PF6): Yield: 95 %. 1H NMR
(300 MHz, DMSO d6): δ (ppm) 9.97 (d, J = 5.2 Hz, 2H), 9.21 (d, J = [(η6-benzene)Ru(phen)(OTf)](OTf): Yield: 93 %. 1H NMR (300 MHz,
9.0 Hz, 2H), 8.31 (d, J = 8.3 Hz, 2H), 8.28–8.15 (m, 2H), 7.76 (d, J = CD3OD): δ (ppm) 10.15 (d, J = 5.3 Hz, 2H), 9.04 (d, J = 8.2 Hz, 2H),
8.5 Hz, 2H), 6.33 (s, 6H), 0.27 (s, 9H). ESI-MS: m/z 607.2 [M-PF6]+.
8.46 (s, 2H), 8.34 (dd, J = 8.2, 5.1 Hz, 2H), 6.35 (s, 6H). ESI-MS:
m/z 508.7 [M-OTf]+, 179.4 [M-2OTf]2+
.
General Procedure for the Synthesis of [(η6-p-cymene)Ru-
(N^N)Cl](PF6) (N^N = bpy, phen, phenamine, phendione, dppz)
[(η6-p-cymene)Ru(phen)(OTf)](OTf): Yield: 91 %. 1H NMR
(300 MHz, CD3OD): δ (ppm) 10.19 (d, J = 5.3 Hz, 2H, 9.02 (d, J =
8.3 Hz, 2H), 8.35–8.20 (m, 4H), 6.57 (d, J = 6.4 Hz, 2H), 6.37 (d, J =
6.4 Hz, 2H), 2.58 (hept., 1H), 2.29 (s, 3H), 0.97 (d, J = 6.9 Hz, 6H). ESI-
A solution of [(η6-p-cymene)RuCl2]2 (150 mg, 0.25 mmol) and N^N
ligand (0.5 mmol) in methanol (50 mL) was heated to reflux over-
night. Solvent was removed under reduced pressure and the result-
ing precipitate dissolved in water (5 mL). Dropwise addition of a
saturated KPF6 aqueous solution gave a dark to bright yellow solid,
which was collected, washed thoroughly with water (5 x 10 mL),
diethyl ether (3 x 10 mL) and finally dried under vacuum.
[(η6-p-cymene)Ru(bpy)Cl] (PF6): Yield: 89 %. 1H NMR (300 MHz,
CD3CN): δ (ppm) 9.32 (d, J = 5.6 Hz, 2H), 8.31 (d, J = 8.1 Hz, 2H),
8.18 (t, J = 7.9 Hz, 2H), 7.69 (t, J = 6.6 Hz, 2H), 5.91 (d, J = 6.3 Hz,
2H), 5.71 (d, J = 6.3 Hz, 2H), 2.65 (hept., 1H), 2.20 (s, 3H), 1.02 (d,
J = 6.9 Hz, 6H). ESI-MS: m/z 427.1 [M-PF6]+.
[(η6-p-cymene)Ru(phen)Cl] (PF6): Yield: 90 %. 1H NMR (300 MHz,
CD3CN): δ (ppm) 9.66 (d, J = 5.3 Hz, 2H), 8.75 (d, J = 8.3 Hz, 2H),
8.15 (s, 2H), 8.03 (dd, J = 8.2, 5.3 Hz, 2H), 6.02 (d, J = 6.3 Hz, 2H),
5.83 (d, J = 6.3 Hz, 2H), 2.69 (hept., 1H), 2.17 (s, 3H), 1.00 (d, J =
6.9 Hz, 6H). ESI-MS: m/z 451.1 [M-PF6]+.
MS: m/z 564.9 [M-OTf]+, 207.4 [M-2OTf]2+
.
[(η6-benzene)Ru(phenamine)(OTf)](OTf): Yield: 92 %. 1H NMR
(300 MHz, CD3OD): δ (ppm)10.21 (d, J = 5.1 Hz, 1H), 9.45 (d, J =
5.3 Hz, 1H), 8.92 (d, J = 8.2 Hz, 1H), 8.53 (d, J = 8.5 Hz, 1H), 8.26 (dd,
J = 8.2, 5.4 Hz, 1H), 8.02 (dd, J = 8.2, 5.4 Hz, 1H), 7.16 (s, 1H), 6.23
(s, 6H), 5.62 (s, 2H). ESI-MS: m/z 525.5 [M-OTf]+, 187.2 [M-2OTf]2+
.
[(η6-p-cymene)Ru(phenamine)(OTf)](OTf): Yield: 93 %. 1H NMR
(300 MHz, CD3OD): δ (ppm)10.04 (d, J = 5.2 Hz, 1H), 9.47 (d, J =
5.3 Hz, 1H), 8.95 (d, J = 8.2 Hz, 1H), 8.52 (d, J = 8.1 Hz, 1H), 8.12 (dd,
J = 8.4, 5.4 Hz, 1H), 7.95 (dd, J = 8.1, 5.2 Hz, 1H), 7.36 (s, 1H), 6.19
(s, 2H), 6.02 (s, 2H), 5.73 (s, 2H), 2.63 (s, 1H), 2.24 (s, 3H), 1.02 (dd,
J = 6.9, 3.1 Hz, 6H). ESI-MS: m/z 579.6 [M-OTf]+, 215.3 [M-2OTf]2+
.
General Procedure for the Synthesis of [Ru(4,4′-(CH2PO3Et2)2-
bpy)2(N^N)](PF6)2 by the Organometallic Route
[(η6-p-cymene)Ru(phenamine)Cl] (PF6): Yield: 94 %. 1H NMR
(300 MHz, CD3CN): δ (ppm) 9.63 (d, J = 5.3 Hz, 1H), 9.26 (d, J =
5.2 Hz, 1H), 8.73 (d, J = 8.4 Hz, 1H), 8.30 (d, J = 8.4 Hz, 1H), 7.98 (dd,
J = 8.5, 5.3 Hz, 1H), 7.77 (dd, J = 8.3, 5.2 Hz, 1H), 7.04 (s, 1H), 5.97
Method A (thermal conditions): A
solution of [(η6-arene)-
Ru(N^N)Cl](PF6) (150 mg, 1 equivalent) and 4,4′-(CH2PO3Et2)2-bpy (2
to 2.3 equivalents) in a mixture of water (9 mL) and 2-methoxy-
ethanol (36 mL) was refluxed overnight. After cooling down to
Eur. J. Inorg. Chem. 0000, 0–0
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