Vibrational spectra of bis(dmit) complexes of main group metals: IR, Raman and ab initio calculations

This work reports a theoretical-experimental investigation of the infrared/Raman vibrational spectra of several metal 1,3-dithole-2-thione-4,5-dithiolate (dmit) complexes; [NEt4]2[Zn(dmit)2], [NEt4][Sb(dmit)2] and [NEt4][Bi(dmit)2]. IR/Raman spectra of all the solids and the solution IR spectrum of...

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Bibliographic Details
Published inJournal of the Brazilian Chemical Society Vol. 15; no. 6; pp. 951 - 963
Main Authors Ferreira, Glaucio B., Comerlato, Nadia M., Wardell, James L., Hollauer, Eduardo
Format Journal Article
LanguageEnglish
Published Sociedade Brasileira de Química 01.12.2004
Subjects
CHEMISTRY, MULTIDISCIPLINARY
ab initio
RHF
DFT
Zn
Bi
IR
Raman
dmit complexes
MP2
Sb
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Summary:This work reports a theoretical-experimental investigation of the infrared/Raman vibrational spectra of several metal 1,3-dithole-2-thione-4,5-dithiolate (dmit) complexes; [NEt4]2[Zn(dmit)2], [NEt4][Sb(dmit)2] and [NEt4][Bi(dmit)2]. IR/Raman spectra of all the solids and the solution IR spectrum of [NEt4]2[Zn(dmit)2] were recorded from 4000 to 100 cm-1. Two regions were clearly identified: below 380 cm-1, the modes presented significant metal-ligand contributions, and above, the modes indicated major ligand contributions. IR/Raman spectra of NEt4Br have also been recorded. The vibrational bands have been assigned starting from the analysis of related compounds, of previous published spectra and compared to several ECPs (SBK, Stuttgart), basis sets (with and without functions d) and methodologies (RHF, MP2 and DFT). Geometries, frequencies and intensities were calculated and compared to the experimental frequencies seeking secure assignment. Thus, an excellent agreement was obtained for several experimental bands.
ISSN:0103-5053
1678-4790
DOI:10.1590/S0103-50532004000600025