Compound RuII
bis(4,4'-dimethyl-2,2'-bipyridine)(4,4'-dicarboxylic acid-2,2'-bipyridine)ruthenium(II) bis(hexafluorophosphate)
Synthetic procedure: See article for the definitive version of this procedure and for full experimental details.
In a 25 mL round bottom flask, a mixture of RuCl2(DMSO)4 (242 mg, 0.500 mmol), dmb (184 mg, 1.00 mmol), lithium chloride (72 mg, 1.7 mmol), dimethylformamide (3 mL, used as received) was sparged with nitrogen. Under a blanket of nitrogen, the mixture was refluxed overnight while being stirred. After cooling to room temperature, 20 mL of acetone was added and the mixture was stored in a freezer at -18 °C. A dark green precipitate was collected via centrifugation. The precipitate was rinsed with water and centrifuged again. The precipitate was further rinsed with diethyl ether. The two supernatants were combined and extracted with water and dichloromethane. The dichloromethane layer (purple) was collected and combined with the precipitate and evacuated to dryness. Yield: 183 mg (0.317 mmol, 63%). UV–Vis absorption (acetonitrile) λmax 557, 374, 296 nm (absorbance ratio 1:1.1:5.6).
To 6.3 mL methanol:water (40:60, v/v), cis-Ru(dmb)2Cl2 (144 mg, 0.27 mmol), dcb (61.1 mg, 0.25 mmol) and sodium bicarbonate (75 mg, 0.9 mmol) were introduced, mixed, and freeze–pump–thawed three times. The solution was refluxed overnight under nitrogen with continuous stirring, and then cooled to room temperature where 1 mL of aqueous 1.0 M HPF6 solution was added dropwise under stirring. A dark red precipitate formed and was filtered, rinsed with aqueous 0.1 M HPF6 solution followed by diethyl ether, and evacuated to dryness. The product was further rinsed with water and centrifuged to remove excess HPF6. The precipitate was evacuated to dryness. Yield: 0.163 g (0.163 mmol, 65%). 1H NMR (500.22 MHz, NaOH/D2O) δ 8.82 (d, J = 1.9 Hz, 2H), 8.32 (s, 2H), 8.31 (s, 2H), 7.89 (d, J = 5.8 Hz, 2H), 7.61 (dd, J = 5.8, 1.8 Hz, 2H), 7.57 (d, J = 5.8 Hz, 2H), 7.54 (d, J = 5.8 Hz, 2H), 7.18 (d, J = 5.9 Hz, 2H), 7.15 (d, J = 6.0 Hz, 2H), 2.50 (s, 6H), 2.48 (s, 6H). ESI-MS (TOF): m/z 859.09 ([M – PF6-]+), calculated 859.12.
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347915351
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