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33846134407
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Selected data for 1 and 2 are provided in the Supporting Information.
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Selected data for 1 and 2 are provided in the Supporting Information.
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14
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33846173388
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Synthesis of [DDP]Cl2·2H2O: 2-Picolylchloride hydrochloride was dissolved in water and neutralized with K2CO3 and extracted with dichloromethane. The organic layer was separated and dried with Na2-SO4, and then the CH2Cl2 solution was kept at room temperature after complete evaporation of solvent pale yellow crystals was formed. Synthesis of 1: 0.118 g of NiCl2·6H2O (0.5 mmol) was dissolved in 10 mL of a MeOH/H2O (1:1) mixture. To this solution, 0.186 g of Na2mnt (1 mmol) was added and it was then stirred for 10 min at room temperature. This reaction mixture was treated with an aqueous solution of [DDP]Cl2·2H2O 0.145 g and 0.5 mmol, whereby a red precipitate was immediately formed, which was separated by filtration. The precipitate was washed with ether and dried in air. It was then crystallized from dime
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2O (0.145 g and 0.5 mmol), whereby a red precipitate was immediately formed, which was separated by filtration. The precipitate was washed with ether and dried in air. It was then crystallized from dimethylformamide (DMF) by slow ether diffusion. The crystals of 1 were separated and washed with ether and dried at room temperature. Yield 0.187 g (51 %). Synthesis of 2: This was synthesized by the same preparation as described for compound 1 (see Supporting Information for details).
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15
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33846144447
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Crystal data of 1: C32H18N8NiO 2S4, M, 733.49 g mol-1, monoclinic, space group C2/c, a, 24.980(4) Å, b, 6.4802(10) Å, c, 21.104-(3) Å, β, 118.107(2)°, U, 3013.2(8) Å3 Z, 4, DC, 1.617 g cm-3, μ, 0.969 mm-1, F(000, 1496. crystal size, 0.44 x 0.12 x 0.08 mm3. 13 804 measured with 2660 unique reflections (Rint, 0.0309, of which 2120 (I > 2σ(I, were used for the structure solution. Final R1, 0.0671, 218 parameters. The final Fourier difference synthesis showed minimum and maximum peaks of -0.196 and, 0.433 e Å-3. Unit cell parameters for compound 2: monoclinic, a, 24.866(5) Å, b, 6.412(10) Å, c, 21.322(14) Å, β, 117.17(3)°, U, 3025.1
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3.
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16
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33845376681
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