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001-es BibID:BIBFORM114075
035-os BibID:(cikkazonosító)122233 (WoS)001024543100001 (Scopus)85162926390
Első szerző:Łyczko, Krzysztof
Cím:Striking stability of a mixed-valence thallium(III)-thallium(I) complex in some solvents / Łyczko, Krzysztof; Wiȩckowska, Agnieszka; Bajnoczi, Éva G.; Csupász, Tibor; Purgel, Mihály; Sigfridsson Clauss, Kajsa G. V.; Tóth, Imre; Persson, Ingmar
Dátum:2023
ISSN:0167-7322
Megjegyzések:At the dissolution of solid anhydrous thallium(III) trifluoromethanesulfonate, Tl(CF3SO3)3, or thallium(III) trifluoroacetate, Tl(CF3COO)3, in dimethylsulfoxide (dmso) or N,N,N',N'-tetramethylurea (tmu), intensely red-colored complexes are formed. This red thallium complex is stable for years in dmso, while it is reduced fairly rapidly to thallium(I) in tmu with a half-life time of an hour. At the dissolution of Tl(CF3SO3)3 in N,N-dimethylpropyleneurea (dmpu) an immediate reduction to thallium(I) takes place. A stable colorless aqueous thallium(III) solution is obtained at the dissolution in acidic water. Stable dmso solutions and solid dmso solvates of thallium(III) perchlorate, nitrate and trifluormethanesulfonate can be prepared by adding dmso to concentrated acidic aqueous thallium(III) solutions. These experimental observations conclude that the pure solids Tl(CF3SO3)3 and Tl(CF3COO)3 play an essential role in the formation of the red-colored thallium complexes. 205Tl NMR data show that the red thallium complex contains equal amounts of thallium(III) and thallium(I). The structure of the red thallium complex in dmso, as determined by EXAFS, has Tl?O bond distances of 2.216(3) and 2.80(2) ?A, which are in very close agreement with the bond distances obtained in the pure dmso solvates of the thallium(III) and thallium(I) ions, respectively, and a Tl???Tl distance of 3.49(1) ?A bridged by oxygen atoms. From the EXAFS data it is impossible to distinguish if dmso molecules and/or trifluoromethanesulfonate ions act as bridges. DFT calculations could eliminate some structures due to the irrelevant structural parameters or the energetics of the proposed reactions.
Tárgyszavak:Természettudományok Kémiai tudományok idegen nyelvű folyóiratközlemény külföldi lapban
folyóiratcikk
Mixed-valence thallium(III)-thallium(I) complex
Dimethylsulfoxide
Red-colored complex
N, N, N'N'-tetramethyl urea
Structure
Decomposition rate
Megjelenés:Journal Of Molecular Liquids. - 385 (2023), p. 1-9. -
További szerzők:Wiȩckowska, Agnieszka Bajnoczi Éva G. Csupász Tibor (1991-) (vegyész) Purgel Mihály (1982-) (vegyész) Sigfridsson Clauss, Kajsa G. V. Tóth Imre (1950-) (vegyész) Persson, Ingmar
Pályázati támogatás:TAMOP-4.2.2.C-11/1/KONV-2012-0010
TÁMOP
NKFIH K-128201
Egyéb
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