Reactions and structures in the gallium(III)/indium(III)-N,N-dimethylthioformamide systems

Topel O., Persson I., Lundberg D., Ullstrom A.

INORGANICA CHIMICA ACTA, cilt.365, sa.1, ss.220-224, 2011 (SCI-Expanded) identifier identifier

  • Yayın Türü: Makale / Tam Makale
  • Cilt numarası: 365 Sayı: 1
  • Basım Tarihi: 2011
  • Doi Numarası: 10.1016/j.ica.2010.09.011
  • Dergi Adı: INORGANICA CHIMICA ACTA
  • Derginin Tarandığı İndeksler: Science Citation Index Expanded (SCI-EXPANDED), Scopus
  • Sayfa Sayıları: ss.220-224
  • Anahtar Kelimeler: Gallium(III), Indium(III), N,N-dimethylthioformamide (DMTF), EXAFS, X-RAY-DIFFRACTION, IONS, N,N-DIMETHYLTHIOFORMAMIDE, MERCURY(II), SCATTERING, CRYSTAL, CADMIUM(II), ABSORPTION, ZINC(II), LIQUIDS
  • Akdeniz Üniversitesi Adresli: Evet

Özet

The structure of the N,N-dimethylthioformamide (DMTF)solvated gallium(III)ion has been determined in solution by means of extended X-ray absorption fine structure (EXAFS)spectroscopy. The gallium(III) ion is four-coordinate in tetrahedral fashion with a mean Ga-S bond distance of 2.233(2)angstrom in DMTF solution. At the dissolution of indium(III)perchlorate or trifluoromethanesulfonate in DMTF coordinated solvent molecules are partly reduced to sulfide ions, and a tetrameric complex with the composition [In4S4(SHN(CH3)(2))(12)](4+) is formed. The structure of the solid tetrameric complex in the perchlorate salt was solved with single crystal X-ray diffraction. Four indium(III)ions and four sulfide ions form a highly symmetric heterocubane structure where each indium binds three bridging sulfide ions and each sulfide ion binds three indium(III)ions with a mean In-S bond distance of 2.584(1)angstrom, and S-In-S angles of 90.3(1)degrees. Each indium(III)additionally binds three DMTF molecules at significantly longer mean In-S bond distance, 2.703(1)angstrom; the S-In-S angles are in the range 80.3-90.4 degrees. Large angle X-ray scattering data on a DMTF solution of indium(III)trifluoromethanesulfonate show that the same tetrameric species characterized in the solid state is also present in solution, whereas the EXAFS measurements only give information about the In-S bond distances due to the short core hole lifetime. (C) 2010 Elsevier B. V. All rights reserved.

The structure of the N,N-dimethylthioformamide (DMTF)solvated gallium(III)ion has been determined in solution by means of extended X-ray absorption fine structure (EXAFS)spectroscopy. The gallium(III) ion is four-coordinate in tetrahedral fashion with a mean Ga-S bond distance of 2.233(2)angstrom in DMTF solution. At the dissolution of indium(III)perchlorate or trifluoromethanesulfonate in DMTF coordinated solvent molecules are partly reduced to sulfide ions, and a tetrameric complex with the composition [In4S4(SHN(CH3)(2))(12)](4+) is formed. The structure of the solid tetrameric complex in the perchlorate salt was solved with single crystal X-ray diffraction. Four indium(III)ions and four sulfide ions form a highly symmetric heterocubane structure where each indium binds three bridging sulfide ions and each sulfide ion binds three indium(III)ions with a mean In-S bond distance of 2.584(1)angstrom, and S-In-S angles of 90.3(1)degrees. Each indium(III)additionally binds three DMTF molecules at significantly longer mean In-S bond distance, 2.703(1)angstrom; the S-In-S angles are in the range 80.3-90.4 degrees. Large angle X-ray scattering data on a DMTF solution of indium(III)trifluoromethanesulfonate show that the same tetrameric species characterized in the solid state is also present in solution, whereas the EXAFS measurements only give information about the In-S bond distances due to the short core hole lifetime.