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 | Sciact - CRIS-system of Boreskov Institute of Catalysis

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 Full article

Journal

Chemische Berichte (now European Journal of Inorganic Chemistry)
ISSN: 0009-2940

Output data

Year: 2022, Volume: 2022, Number: 33, Article number : e202200463, Pages count : 10 DOI: 10.1002/ejic.202200463

Authors

Rudnitskaya Olga V. ¹ , Tereshina Tatiana A. ¹ , Dobrokhotova Ekaterina V. ¹ , Kultyshkina Ekaterina K. ¹ , Yakushev Ilya A. ² , Chumakova Natalia A. ^3,4 , Kokorin Alexander I. ^3,5 , Zubavichus Yan V. ⁶ , Khrustalev Victor N. ^1,7

Affiliations

1	Department of Inorganic Chemistry, Peoples' Friendship University of Russia (RUDN University), 6 Miklukho-Maklay St, 117198 Moscow, Russian Federation
2	Kurnakov Institute of General and Inorganic Chemistry RAS, Leninsky prospect, 31, 119991 Moscow, Russian Federation
3	Semenov Federal Research Center for Chemical Physics RAS, Kosygin st., 4, 119991 Moscow, Russian Federation
4	Chemistry Department, Lomonosov Moscow State University, Leninskie gory, 2, 119991 Moscow, Russian Federation
5	Plekhanov Russian University of Economics, Stremyanny per., 36, 117997 Moscow, Russian Federation
6	Synchrotron Radiation Facility SKIF, Boreskov Institute of Catalysis SB RAS, Nikolskii pr. 1, 630559 Koltsovo, Russian Federation
7	Zelinsky Institute of Organic Chemistry RAS, Leninsky prospect, 47, 119991 Moscow, Russian Federation

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.

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.
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
Chemische Berichte (now European Journal of Inorganic Chemistry). 2022. V.2022. N33. e202200463 :1-10. DOI: 10.1002/ejic.202200463 WOS Scopus ANCAN OpenAlex publication_identifier_short.sciact_skif_identifier_type

Submitted:	Jul 20, 2022
Accepted:	Sep 13, 2022
Published online:	Sep 13, 2022
Published print:	Nov 15, 2022

Web of science:	WOS:000871911500001
Scopus:	2-s2.0-85141128593
Chemical Abstracts:	2022:2761865
Chemical Abstracts (print):	181:111629
OpenAlex:	W4296020765
publication_identifier.sciact_skif_identifier_type:	563

DB	Citing
OpenAlex	1
Scopus	3
Web of science	3