, mmol) was solubilised in the solvent mixture ethanol/water (125:30, 155 mL) previously degassed with argon. The reaction mixture was stirred at 100 °C and obtained a dark blue colour in 4-5 h. At this time, dbm (3.7 g, 16.5 mmol) and acac (0.844 mL, 8.2 mmol) were added to the cooled solution. TLC was used to check the reaction on Silica with toluene. The solution was refluxed for an additional 2 hours. Then, the mixture was cooled again and KHCO3 (1.25 g, 12.5 mmol) was added to the green solution. A release of gas was observed. During the night, the solution turned to orange and in the morning, it was cooled to add another portion of KHCO3 (1.23 g, 12.3 mmol) The solution was put under reflux yet again for 4 h, and then the last portion of KHCO3 (1.24 g, 12.4 mmol) was added to the cooled solution. A black precipitate gradually appeared with the addition of KHCO3. The heating and the stirring were held constant for a second night. The reaction was stopped after 48 hours. The solvents were evaporated and the black precipitate purified using column chromatography on Silica with a mixture of hexane, Three products were collected : first, [Ru(dbm)3] 1 (black powder, yield: 17 %, 1.1 g), second, [Ru(dbm)2(acac)] 2 (crimson powder, yield: 35 %, 1.9 g) and third, [Ru(dbm)(acac)2] 3 (dark red crystals, yield: 4 %, 0.16 g). [Ru(dbm), p.40
, e (NBS) was solubilised in dichloromethane and was added dropwise to the 0.1 V.s -1 , vs.SCE) E1, Ru, 13.0. Mass spectroscopyRu III /Ru II ) = -0.689 V, |?E| = 0.073 V, E1Ru III /Ru IV ) = 0.995 V, |?E| = 0.076 V. UV-Vis4H, s, Hi), 12.04 (4H, s, Hc), 9.81 (2H, t, J = 6.9 Hz Hz, Hj), 6.42 (4H, d, J = 6.8 Hz, Hb), -0.80 (6H, s, Hl), -22.75 (1H, s, Hn), -37.02 (2H, s, Hf). 13 C NMR, pp.1520-332
, CV (DCM, 0.1 M TBAH, 0.1 V.s -1 -4.86 (6H, s, Hl), -26.91 (2H, s, Hn), -39.61 (1H, s, Hf), 13 C NMR (CD2Cl2, ? = 53.7 ppm) 138 Preparation of [Ru(dbm)2(acac-I)] 5 and [Ru(dbm)2(acac-Br)] 6. [Ru(dbm)2(acac-I)] 5 was obtained by a direct substitution on the 3-position of the acac ligand of25 g, 0.4 mmol) was solubilised in toluene, and the solution was degassed with argon. 0.18 g (0.78 mmol) of N-iodosuccinimide (NIS) was added and the mixture was stirred at r.t.. The solution was dark orange. After 1 hour, as no evolution appeared on the TLC plates (Silica, toluene), the mixture was refluxed. The solution became darker (black with red gleams). 1 hour after refluxing, 0.17 g (0.77 mmol) of NIS was added. 1 hour later a last portion of NIS (0.18 g, 0.79 mmol) was added. The reaction was stopped after 4 hours. To remove the excess iodine, 25 mL of an aqueous solution (0.5 M) of sodium thiosulfate were added. Then, the mixture was extracted with ca. 5 ? 40 mL of toluene and ca. 4 ? 100 mL of distilled water to wash the organic phase. All of the extracted organic portions were consolidated and the toluene was evaporated. The crude product was purified using column chromatography on Silica with toluene. Dark purple crystals were obtained with a yield of 77 % (0.2 g), Mass spectroscopy 229 (13.5). 1 H NMR (CD2Cl2, ? = 5.32 ppm) 13.06 (4H, s, Hc), 9.94 (2H, t, J = 6.9 Hz, Ha), 6.64 (4H, d, J = 6.8 Hz, Hb), -2.46 (6H, s, Hp)Ru(dbm)2(acac)]. [Ru(dbm)2(acac)] 2 (0Acac-I] + , 423 [M- Dbm-I] + . IR (KBr) ?/cm -1 1509 (C=O), pp.523-522
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