Chemical 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 Analogue

An iridium complex [H(dmso)2]2[IrCl6] (1) is synthesized via the reaction of H2IrCl6 with DMSO in an acetone solution. The substance 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 (CIr=n ⋅ 10−2−n ⋅ 10−4 M) are allowed to age in ambience. In the case of acetone solutions, the reduction is accompanied by the incorporation of DMSO molecules into the coordination sphere of Ir giving rise to trans-[IrIIICl4(dmso)2]−. In parallel, protonated DMSO shows reactivity towards acetone to afford dimethylacetonylsulfonium cations. Red crystals of [Me2SCH2C(O)Me]2[IrCl6] (2), orange crystals of [Me2SCH2C(O)Me][IrCl4(dmso)2] (3), and yellow crystals of [H(dmso)][IrCl4(dmso)2] (4) were isolated from aged acetone solutions of 1 and studied by X-ray crystallography. In the crystal structures of 2 and 3, dimethylacetonylsulfonium act as the cationic parts of the complexes. Meanwhile, the protonated form of DMSO, hydroxy(dimethyl)sulfonium, is found in 4. A similar aging procedure applied to an acetone solution of Os-based analogue [H(dmso)2]2[OsCl6] afforded a novel osmium complex [Me2SCH2C(O)Me]2[OsCl6] (5), which was proven to be isostructural to 2. © 2022 Wiley-VCH GmbH.

Авторы
Rudnitskaya O.V. , Tereshina T.A. , Dobrokhotova E.V. , Kultyshkina E.K. , Yakushev I.A. , Chumakova N.A. , Kokorin A.I. , Zubavichus Y.V. , Khrustalev V.N.
Издательство
Wiley-VCH Verlag
Номер выпуска
33
Язык
Английский
Статус
Опубликовано
Номер
e202200463
Том
2022
Год
2022
Организации
  • 1 Department of Inorganic Chemistry, Peoples' Friendship University of Russia (RUDN University), 6 Miklukho-Maklay St, Moscow, 117198, Russian Federation
  • 2 Kurnakov Institute of General and Inorganic Chemistry RAS, Leninsky prospect, 31, Moscow, 119991, Russian Federation
  • 3 Semenov Federal Research Center for Chemical Physics RAS, Kosygin st., 4, Moscow, 119991, Russian Federation
  • 4 Chemistry Department, Lomonosov Moscow State University, Leninskie gory, 2, Moscow, 119991, Russian Federation
  • 5 Plekhanov Russian University of Economics, Stremyanny per., 36, Moscow, 117997, Russian Federation
  • 6 Synchrotron Radiation Facility SKIF, Boreskov Institute of Catalysis SB RAS, Nikolskii pr. 1, Koltsovo, 630559, Russian Federation
  • 7 Zelinsky Institute of Organic Chemistry RAS, Leninsky prospect, 47, Moscow, 119991, Russian Federation
Ключевые слова
Dimethylacetonylsulfonium cation; DMSO ligand; Iridium complexes; Spectrophotometry; X-ray diffraction
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