Сhemical evolution in solutions of Ir complex [H(dmso)2]2[IrCl6]. Structures of [H(dmso)2]2[IrCl6], [H(dmso)][IrCl4(dmso)2], [Me2SCH2C(O)Me][IrCl4(dmso)2], [Me2SCH2C(O)Me]2[IrCl6] and its Os analogueстатья
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Аннотация:An iridium complex [H(dmso)2]2[IrCl6] (1) is synthesized viathe reaction of H2IrCl6 with DMSO in an acetone solution. Thesubstance is thoroughly characterized using UV-Vis, ATR-FTIR, NMR,and EPR spectroscopies, single-crystal and powder X-ray diffraction.Iridium undergoes a slow spontaneous reduction to the chemical state+3 when solutions of 1 in water, hydrochloric acid, or acetone (СIr =n·10-2 - n·10-4 M) are allowed to age in ambience. In the case ofacetone solutions, the reduction is accompanied by the incorporationof DMSO molecules into the coordination sphere of Ir giving rise totrans-[IrIIICl4(dmso)2]-. In parallel, protonated DMSO shows reactivitytowards acetone to afford dimethylacetonylsulfonium cations. Redcrystals of [Me2SCН2C(O)Me]2[IrCl6] (2), orange crystals of[Me2SCН2C(O)Me][IrCl4(dmso)2] (3), and yellow crystals of[H(dmso)][IrCl4(dmso)2] (4) were isolated from aged acetone solutionsof 1 and studied by X-ray crystallography. In the crystal structures of2 and 3, dimethylacetonylsulfonium act as the cationic parts of thecomplexes. Meanwhile, the protonated form of DMSO,hydroxy(dimethyl)sulfonium, is found in 4. A similar aging procedureapplied to an acetone solution of Os-based analogue[H(dmso)2]2[OsCl6] afforded a novel osmium complex[Me2SCН2C(O)Me]2[OsCl6] (5), which was proven to be isostructuralto 2.
