C-13- and P-31-NMR study of tetracarbonylbis(diphenylphosphino)alkanemetal(0) complexes of the group 6 elements

Ozer Z., Ozkar S.

TURKISH JOURNAL OF CHEMISTRY, vol.23, no.1, pp.9-14, 1999 (SCI-Expanded) identifier

  • Publication Type: Article / Article
  • Volume: 23 Issue: 1
  • Publication Date: 1999
  • Journal Name: TURKISH JOURNAL OF CHEMISTRY
  • Journal Indexes: Science Citation Index Expanded (SCI-EXPANDED), Scopus, TR DİZİN (ULAKBİM)
  • Page Numbers: pp.9-14
  • Keywords: chromium, molybdenum, tungsten, carbonyl, diphosphine, NMR, METAL-CARBONYL-COMPLEXES, BIS-PHOSPHORUS LIGANDS, NUCLEAR MAGNETIC-RESONANCE, DITERTIARY PHOSPHINES, MO, ISOMERIZATION, DERIVATIVES, SYSTEMS, CR
  • Middle East Technical University Affiliated: Yes

Abstract

Tetracarbonylbis(diphenylphosphino)alkanemetal(0) complexes of the general formula M(CO)(4)[(C-6 H-5)(2) P (CH2)(n) P(C6H5)(2)] (M: Cr, Mo, W; n: 1, 2, 3) were synthesized from the reaction of M(CO)(4) (eta(2:2)-1,5-cyclooctadiene) with the appropriate ligand and characterized by means of IR and NMR (C-13 and P-31) spectroscopy Spectroscopic data shows that two phosphorus atoms in the complexes are identical and occupy two cis-coordiantion sites in a pseudo-octahedral coordination sphere of the metal. The comparative study of the coordination shift and the P-31-C-13 coupling constant reveals that two carbonyl groups trans to one of two phosphorus atoms in the diphosphine ligand are shifted toward the lower magnetic field more than those which are cis to both phosphorus atoms. This is ascribed to the fact that two multiface ligands such as carbonyl or phosphine compete for the use of metal d(pi)-orbitals more strongly when they are trans to each other.