Coordinated 2-halo-l,3,2-dioxaphosphorinane ligands. I. syntheses and 13C, 17O, 31P and 95Mo NMR and IR spectroscopic characterization of some molybdenum pentacarbonyl complexes of 2-substituted-5, 5-dimethyl-1,3, 2-dioxaphosphorinanes

Academic Article

Abstract

  • A study of the reactions of Mo(CO) (P(OCH - CMe CH 0)X) (X = C1, Br) with a variety of nucleophiles of the type HER (E = NH, O, S; R = H, alkyl, aryl) is reported. The mechanism of these reactions is shown to be S 2, and the significantly slower rates of reactions of n-propylamine with the above complexes relative to the rate of reaction of n-propylamine with Mo(CO) (Ph PC1) is discussed. The C, O, P and Mo NMR data and infrared data for these complexes are presented. Good correlations between chemical shifts of the cis and trans CO C and trans CO 0 NMR resonances, CO infrared stretching force constants and the magnitudes of J and J (trans CO) are observed and the reasons for these correlations are discussed. The correlations between the chemical shifts of NMR-active nuclei in the Mo(CO) (P(OCH CMe - CH O)ER) complexes with the chemical shifts of similar nuclei in the Mo(CO) (Ph PER) complexes fange from excellent to very poor. This indicates that the effects of-the P-substituents on the chemical shifts of the NMR-active nuclei in these complexes are not additive. © 1986. 5 2 2 2 N 5 2 Mop PC 5 2 2 2 5 2 13 17 31 95 13 17 1 2
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    Author List

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

  • 21
  • End Page

  • 30
  • Volume

  • 116
  • Issue

  • 1