Coordinated 2-halo-1,3,2-dioxaphosphorinane ligands. II. Syntheses and 13C, 31P and 95Mo NMR and IR spectroscopic characterization of some Cr and Mo pentacarbonyl complexes of 2-substituted-4-methyl-1,3,2-dioxaphosphorinanes

Academic Article


  • A study of the reactions of M(CO)5(P(OCH2CH2CH(Me)O)Cl) (M=Cr, Mo) with a variety of nucleophiles of the type HER (E=NH, O, S; R=H, alkyl, aryl) is reported. The 13C, 31P and 95Mo NMR and IR spectral data for the M(CO)5(P(OCH2CH2CH(Me)O)ER) complexes is presented and compared to that previously reported for some Mo(CO)5(P(OCH2CMe2CH2O)ER) complexes. This comparison provides insight into the manner in which variations in the metal and in the substitution on the 1,3,2-dioxaphosphorinane ring affect the electron density distribution within these complexes. The results from a study of the rates of chloride substitution by n-propylamine in the M(CO)s(P(OCH2CH2CH(Me)O)Cl) complexes are also presented. These rates are compared with those previously reported for chloride substitution by n-propylamine in the Mo(CO)5(P(OCH2CMe2CH2O)Cl) and Mo(CO)5(Ph2PCl) complexes. These comparisons, in conjunction with the NMR and IR studies, suggest that both the position of the Me groups on the phosphorinane ring and the amount of electron density on the P have significant effects upon the rate of chloride substitution in these complexes. © 1986.
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    Author List

  • Gray GM; Whitten JE; Box JW
  • Start Page

  • 25
  • End Page

  • 32
  • Volume

  • 120
  • Issue

  • 1