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] | Sciact - CRIS-system of Boreskov Institute of Catalysis

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] Full article

Journal

ACS Omega
ISSN: 2470-1343

Output data

Year: 2023, Volume: 8, Number: 23, Pages: 20569-20578 Pages count : 10 DOI: 10.1021/acsomega.3c01012

Authors

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

Affiliations

1	Department of Inorganic Chemistry, Peoples’ Friendship University of Russia (RUDN University), Moscow 117198, Russian Federation
2	Zelinsky Institute of Organic Chemistry RAS, Moscow 119991, Russian Federation
3	Chemistry Department, Lomonosov Moscow State University, Moscow 119991, Russian Federation
4	Semenov Federal Research Center for Chemical Physics RAS, Moscow 119991, Russian Federation
5	Synchrotron Radiation Facility SKIF, Boreskov Institute of Catalysis SB RAS, Koltsovo 630559, Russian Federation

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.

Rudnitskaya O.V. , Tereshina T.A. , Dobrokhotova E.V. , Kultyshkina E.K. , Chumakova N.A. , Kokorin A.I. , Zubavichus Y.V. , Khrustalev V.N.
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]
ACS Omega. 2023. V.8. N23. P.20569-20578. DOI: 10.1021/acsomega.3c01012 WOS Scopus ANCAN PMID OpenAlex publication_identifier_short.sciact_skif_identifier_type

Submitted:	Feb 15, 2023
Accepted:	May 11, 2023
Published online:	May 27, 2023
Published print:	Jun 13, 2023

Web of science:	WOS:001006687700001
Scopus:	2-s2.0-85162863217
Chemical Abstracts:	2023:1081255
Chemical Abstracts (print):	183:43856
PMID:	37323389
OpenAlex:	W4378575171
publication_identifier.sciact_skif_identifier_type:	577

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Scopus	1
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