^{13}C-and ^{31}P-NMR Study of Tetracarbonylbis(diphenylphosphino)alkanemetal(0) Complexes of The Group 6 Elements


Abstract: Tetracarbonylbis(diphenylphosphino)alkanemetal(0) complexes of the general formula M(CO)_4[(C_6H_5)_2P (CH_2)_nP(C_6H_5)_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 (^{13}C and ^{31}P) 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 ^{31}P-^{13}C 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.

Keywords: Chromium, Molybdenum, Tungsten, Carbonyl, Diphosphine, NMR

Full Text: PDF