* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
Eu(iButCHex)3*3,4,7,8-tetramethylphenanthroline[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
With sodium hydroxide; In ethanol; water;
General procedure: In the preparation of the Ln(CA)3·Phn and Ln(CA)3·Bpy adducts the 3-N NaOH water solution and an ethanol solution of Phn or Bpy were added to an ethanol solution of CA. Then, a water?ethanol (1:1) solution of LnCl3·6H2O was drop by drop added to the previous mixture at heating in a water bath (at 60?70°C) or sometimes without heating. A molar ratio of the reagents CA: Phn (Bpy): lanthanide chloride: NaOH was equal to 3:1:1:3. The compound Eu(AcCHex)3·Phen was also synthesized by other method involving the preparation of an ethanol solution of a mixture of CA, Phen and EuCl3·6H2O in a molar ratio of 3:1:1 and adjusting the pH value of reaction mixture to 6 with a liquid ammonia. It should be pointed out that the heating of the reaction mixture results in a decrease in the keto/enol ratio of cycloalkanone [37] that promotes a binding of CA with the Ln3+ ion. At the same time, the probability of decomposition of cycloalkanonate anion increases.
Under inert gas protection, xylene (10 mL) was added to a 50 mL Schlenk reaction tube.Cuprous bromide (0.036 g, 0.25 mmol), 4,5-bisdiphenylphosphine-9,9-dimethylxanthene (0.36 g, 0.625 mmol), stirred at room temperature for 3 h,Add 3,4,7,8-tetramethyl-1,10-phenanthroline (0.11 g, 0.5 mmol) at room temperature for 5 h.Activated zinc powder (3.0 g, 48 mmol) was added, and dibromomethane (8.1 g, 48 mmol) was added dropwise at -15C.The mixture was heated to reflux for 16 h until the zinc powder was completely reacted and cooled to room temperature to give a milky white suspension.
In 2-methoxy-ethanol; water; at 100℃; for 36h;Inert atmosphere;
General procedure: Preparation of the [Ir(C^N)2(N^N)]3+[PF6-]3: in typical reaction procedure 0.10 g (0.058 mmol) of [{Ir(C^N)2Cl}2]4+[PF6]4, 0.04 g (0.16 mmol) <strong>[26042-63-7]AgPF6</strong> and 0.03-0.06 g (0.19 mmol) of N^N ligand were heated at 100 C under argon in 15 ml of argon-purged 2-methoxyethanol/water mixture (8:2 v/v) for ca. 36 h. After cooling, the reaction mixture to ambient temperature, the precipitated AgCl was filtered off and the solvents were removed by rotary evaporation. The residue was dissolved in small amount of acetone and an excess of [NnBu4]Cl was added. The precipitate was filtered off and washed with acetone. The hexafluorophosphate salts were further obtained by anion metathesis with NH4PF6 in cold water with yields: [Ir(C^N)2(phen)]3+[PF6-]3 64%, [Ir(C^N)2(tmphen)]3+[PF6-]3 81%, [Ir(C^N)2(dpphen)]3+[PF6-]3 53%, [Ir(C^N)2(dpq)]3+[PF6-]3 42%, [Ir(C^N)2(dppz)]3+[PF6-]3 39%, [Ir(C^N)2(dppn)]3+[PF6-]3 57%. For the NMR data see Supporting information.
Stage #1: iridium(III) chloride n-hydrate; 5-methyl-2-(4-fluorophenyl)-pyridine In 2-methoxy-ethanol at 125℃; for 16h;
Stage #2: 3,4,7,8-Tetramethyl-o-phenanthrolin In dimethyl sulfoxide at 150℃; for 16h;
Stage #1: hydrogenchloride; potassium aquapentachlororuthenate(III); 3,4,7,8-Tetramethyl-o-phenanthrolin In water for 0.25h;
Stage #2: With hypophosphorous acid In water for 0.5h; Reflux;
2.2. Synthesis of [Ru(TMP)3]2+
The [Ru(TMP)3]2+ complex was synthesized following previousliterature [44]. Potassium aquopentachlororuthenate(III) (0.5000 g)was dissolved in 50 mL of hot water containing one drop of 6 N hydrochloricacid and the 3,4,7,8-tetramethylphenanthroline (0.9464 g)ligand was added slowly with stirring. The mixture was boiled for 15min until the solution became dark green. Hypophosphorous acid (1.2mL of a 30% solution) was first neutralized with sodium hydroxide (3.5mL of a 2 N solution) and then added into the mixture and reflux 30 minuntil the color of the solution changed from green to deep brown. Themixture was filtered and 10 mL of 6 N hydrochloric acid was added withstirring to the hot filtered solution. The volume of the solution wasreduced until crystals formed. The crude orange red product wasrecrystallized from hot water. The chloride salt of the compound wasprecipitated as racemic ruthenium by H2O.