Ruthenium(II) complexes containing 2-pyridineformamide- and 2-benzoylpyridine-derived thiosemicarbazones and PPh3: NMR and electrochemical studies of cis-trans-isomerization

Spectrochim Acta A Mol Biomol Spectrosc. 2008 Apr;69(4):1277-82. doi: 10.1016/j.saa.2007.07.005. Epub 2007 Jul 17.

Abstract

[RuCl(L)(PPh(3))(2)] complexes with 2-benzoylpyridine- and 2-pyridineformamide-derived thiosemicarbazones (HL) were obtained and fully characterized. The complexes form cis-trans isomers. The cis isomer is disfavored by the sterical effect of two bulky groups close to each other whereas the trans isomer is disfavored by the electronic effect of competition of two phosphorous for pi-bonding d orbitals of the metal. Our results suggest that, although both factors may be operating simultaneously, in CH(2)Cl(2) solution the balance of these counterpoising effects favors the formation of the trans isomer.

MeSH terms

  • Electrochemistry / methods*
  • Formamides / chemistry*
  • Isomerism
  • Magnetic Resonance Spectroscopy
  • Organometallic Compounds / chemistry*
  • Phosphines / chemistry*
  • Pyridines / chemistry*
  • Ruthenium / chemistry*
  • Spectrophotometry, Infrared
  • Thiosemicarbazones / chemistry*

Substances

  • Formamides
  • Organometallic Compounds
  • Phosphines
  • Pyridines
  • Thiosemicarbazones
  • formamide
  • Ruthenium