First Iridium(IV) Chloride-Dimethyl Sulfoxide Complex [H(dmso)2][IrCl5(dmso-κO)]: Synthesis and Structure along with Novel Polymorph Modifications of [H(dmso)2][trans-IrCl4(dmso-κS)2] and [H(dmso)][trans-IrCl4(dmso-κS)2]

As evidenced by UV-Vis and EPR spectroscopies, the reaction of H2IrCl6·6H2O or Na2[IrCl6]·nH2O with DMSO results in a slow reduction of Ir(IV) avoiding the formation of Ir(IV) dimethyl sulfoxide complexes in measurable quantities. More specifically, we successfully isolated and solved the crystal structure of a sodium hexachloridoiridate(III), Na3[IrCl6]·2H2O, as a product of Na2[IrCl6]·nH2O reduction in an acetone solution. Furthermore, it was shown that [IrCl5(Me2CO)]− species is gradually formed in an acetone solution of H2IrCl6·6H2O upon storage. The reaction of DMSO with aged acetone solution of H2IrCl6·6H2O dominated by [IrCl5(Me2CO)]− affords a novel iridium(IV) chloride-dimethyl sulfoxide salt [H(dmso)2][IrCl5(dmso-κO)] (1). The compound was characterized by various spectroscopies (IR, EPR, UV-Vis) and X-ray diffraction techniques applied both to single-crystal and polycrystalline powder. The DMSO ligand is coordinated to the iridium site via the oxygen atom. New polymorph modifications of known iridium(III) complexes [H(dmso)2][trans-IrCl4(dmso-κS)2] and [H(dmso)][trans-IrCl4(dmso-κS)2] were isolated and structurally elucidated as byproducts of the above reaction. © 2023 The Authors. Published by American Chemical Society.

Авторы
Rudnitskaya O.V. , Tereshina T.A. , Dobrokhotova E.V. , Kultyshkina E.K. , Chumakova N.A. , Kokorin A.I. , Zubavichus Y.V. , Khrustalev V.N.
Журнал
Издательство
American Chemical Society
Номер выпуска
23
Язык
Английский
Страницы
20569-20578
Статус
Опубликовано
Том
8
Год
2023
Организации
  • 1 Department of Inorganic Chemistry, Peoples’ Friendship University of Russia (RUDN University), 6 Miklukho-Maklay St, Moscow, 117198, Russian Federation
  • 2 Semenov Federal Research Center for Chemical Physics RAS, Kosygin St., 4, Moscow, 119991, Russian Federation
  • 3 Chemistry Department, Lomonosov Moscow State University, Leninskie Gory, 2, Moscow, 119991, Russian Federation
  • 4 Synchrotron Radiation Facility SKIF, Boreskov Institute of Catalysis SB RAS, Nikolskii Prosp., 1, Koltsovo, 630559, Russian Federation
  • 5 Zelinsky Institute of Organic Chemistry RAS, Leninsky Prosp., 47, Moscow, 119991, Russian Federation
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