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

• Autor(es):

  Ferreira, Glaucio B. (Universidade Federal do Rio de Janeiro. Instituto de Química);

  Comerlato, Nadia M. (Universidade Federal do Rio de Janeiro. Instituto de Química);

  Wardell, James L. (Universidade Federal do Rio de Janeiro. Instituto de Química);

  Hollauer, Eduardo (Universidade Federal Fluminense. Instituto de Química).

• Fonte:

  Journal of the Brazilian Chemical Society; volume 15, número 6, páginas 951-963. Dezembro 2004.

• Assuntos:

  IR;

  Raman;

  ab initio;

  RHF;

  DFT;

  MP2;

  dmit complexes;

  Zn;

  Sb;

  Bi.

• Resumo:

  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.

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