Low-Frequency Vibrational Spectra of Bromo- and Iodobismuthates and the Observation of a Trans Effect

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Abstract

The far-infrared and Raman spectra of 17 bismuth halide complexes of formulas BiX6 3-, BiX5 2-, Bi2X9 3-, and BiX4 - have been recorded for X = Br or I. The spectra of these anions, which show bands only below 200 cm-1, have been analyzed in terms of known structures. Several of the spectra have been used to confirm predicted structures for other molecules. Although the solid-state spectra are seen to vary somewhat with the cation present, they can be used to distinguish between the different types of complexes. These spectra also establish frequency ranges expected for Bi-Br and Bi-I stretches, for both the external and the bridging types. Approximate force constants were calculated for the various types of Bi-X stretches; from these it was determined that the nature of the bonding of the halide trans to a particular Bi-X bond significantly affects the strength of that bismuth-halogen bond. Moreover, the strength of the Bi-X bonds was found to be greatest in the anions in which the largest number of the other bonds were to bridged halogens.

Original languageEnglish (US)
Pages (from-to)44-49
Number of pages6
JournalInorganic Chemistry
Volume19
Issue number1
DOIs
StatePublished - 1980
Externally publishedYes

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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