Tetracarboxylatodirhenium complexes linked by axial cyano bridges to metalpentacarbonyl ligands - Synthesis and characterization

Fritz E. Kühn, Isabel S. Gonçalves, André D. Lopes, João P. Lopes, Carlos C. Romão, Wolfgang Wachter, Janos Mink, Làszló Hajba, A. Jorge Parola, Fernando Pina, João Sotomayor

Research output: Contribution to journalArticle

Abstract

Reaction of Re2{μ-O2CC(CH3)3}4Cl2 with [(CO)5M-CN]Na (M = Cr, Mo, W) leads to tetranuclear complexes of formula Re2{μ- O2CC(CH3)3}4[-NC-M(CO)5]2 (M = Cr, Mo, W). These complexes were characterized by 1H-, 13C-, and 95Mo-NMR, IR and Raman spectroscopy, elemental analysis and examined by cyclic voltammetry. The applied methods show the donor capabilities of the [(CO)5M-CN]- ligands which shift electron density towards the Re centers weakening the Re-Re quadruple bond. The Re-Re bond lengths and the v(Re-Re) force constants are estimated based on the FT-IR and Raman examinations. Photochemical examinations and TG/MS experiments have also been conducted. The latter method shows that the product complexes decompose around 100 °C, by first loosing their carbonyl substituents; as do the Cr, Mo, W precursor compounds. The dirhenium tetrapivalate unit decomposes only at higher temperatures in a distinct second step.

Original languageEnglish
Pages (from-to)295-301
Number of pages7
JournalEuropean Journal of Inorganic Chemistry
Issue number2
DOIs
Publication statusPublished - 1 Jan 1999

Keywords

  • Carboxylate complexes
  • Chromium
  • Metal-metal multiple bonds
  • Molybdenum
  • Rhenium
  • Tungsten

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