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

• 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.

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NATURVETENSKAP  -- Kemi -- Oorganisk kemi (hsv//swe)

NATURAL SCIENCES  -- Chemical Sciences -- Inorganic Chemistry (hsv//eng)

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