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Striking stability of a mixed-valence thallium(III)-thallium(I) complex in some solvents

Journal Article · · Journal of Molecular Liquids
 [1];  [2];  [3];  [4];  [4];  [5];  [4];  [6]
  1. Institute of Nuclear Chemistry and Technology, Warsaw (Poland)
  2. Univ. of Warsaw (Poland)
  3. Swedish Univ. of Agricultural Sciences, Uppsala (Sweden); Wigner Research Center for Physics, Budapest (Hungary)
  4. University of Debrecen (Hungary)
  5. Lund Univ. (Sweden). MAX IV Laboratory
  6. Swedish Univ. of Agricultural Sciences, Uppsala (Sweden
+ Show Author Affiliations

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) Å, 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) Å 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.

Research Organization:
SLAC National Accelerator Laboratory, Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Biological and Environmental Research (BER); European Union (EU); European Social Fund; National Institutes of Health (NIH); National Institute of General Medical Sciences (NIGMS); Swedish Research Council (SRC); Swedish Governmental Agency for Innovation Systems; Formas
Grant/Contract Number:
AC02-76SF00515
OSTI ID:
2423933
Journal Information:
Journal of Molecular Liquids, Journal Name: Journal of Molecular Liquids Vol. 385; ISSN 0167-7322
Publisher:
ElsevierCopyright Statement
Country of Publication:
United States
Language:
English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Chemistry
Dimethylsulfoxide
N
N
N'N'-tetramethyl urea
Physics
decomposition rate
mixed-valence thallium(III)-thallium(I) complex
red-colored complex
structure