Contributions to the coordination and structural chemistry of gallium(III) and indium(III) halides: Complexes with Bi- and tridentate tertiary phosphanes

Marcus Sigl, Annette Schier, Hubert Schmidbaur

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Abstract

The reactions of gallium and indium trihalides with 1,2-bis-(diphenylphosphanyl)benzene (DP) and bis[(2-diphenyl-phosphanyl)phenyl]phenylphosphane (TP) lead to a variety of molecular and ionic complexes. Treatment of InCl3 with DP results in [(DP)2InCl2]+[InCl4]- (1). With InBr3 or InI3 molecular 1:1 complexes (DP)InX3 (2: X = Br, 3: X = I) and ionic 1:2 complexes [(DP)InX2J+[InX4]- (4: X = Br, 5: X = I) are obtained. With GaBr3 and GaI3 only the ionic complexes [(DP)GaX2]+[GaX4]- (6: X = Br, 7: X = I) are generated. According to single-crystal X-ray analyses the environment of the metal center is octahedral in the cation of 1, square pyramidal in 3, and tetrahedral in the cations of 5 and 7. The reactions of TP with GaI3 or InI3 afford ionic complexes [(TP)MI2]+[MI4]- (8: M = Ga, 9: M = In). As shown by 31P-NMR studies and X-ray analyses, TP acts as a bidentate ligand in both complexes. The central phosphorus atom is not engaged in coordinative bonding. The 31P resonances of all compounds appear at higher field as compared to the free ligand. This phenomenon calls for further investigations and a detailed theoretical treatment.

Original languageEnglish
Pages (from-to)203-210
Number of pages8
JournalEuropean Journal of Inorganic Chemistry
Issue number2
DOIs
StatePublished - Feb 1998
Externally publishedYes

Keywords

  • Complexes
  • Crystallography
  • Gallium(III) halides
  • Indium(III) halides
  • Lewis acid catalysis
  • Phosphanes, polydentate

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