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  • Chem Sci Trans., 2015, 4(3),  pp 704-715  

    DOI:10.7598/cst2015.1039

    Research Article

    Oxygen Atom Transfer from Pyridylpyridazine Chelated Oxidorhenium(V) Complex to Diphosphines: Twin Isomerization, Effects of Diphosphine Spacer Length and Metal Oxidation State

  • BIKASH KUMAR PANDA1, BISWARUP MONDAL2, UMASANKAR SENAPATI3 and SUMAN SENGUPTA4*
  • 1Department of Chemistry, Jangipur College, Jangipur, Murshidabad - 742213, W.B., India
    2Department of Chemistry, Sitananda College, Nandigram, Purba Medinipur-721631, W.B., India
    3Department of Chemistry, Santipur College, Santipur, Nadia-741404, W.B., India
    4Department of Chemistry, Ananda Chandra College, Jalpaiguri-735101, W.B., India
  • Abstract

    The bimolecular reaction of ReVOCl3(dppz), 1, (where dppz is 3,6-di(2-pyridyl) pyridazine) with excess diphosphine Ph2P(CH2)xPPh2 (x=1-4) has furnished ReIII(OPPh2 (CH2)x PPh2)Cl3 (dppz), 2 with a dangling phosphine function which is spontaneously converted in solution to ReIII(PPh2 (CH2)xP(O)Ph2)Cl3 (dppz), 3. The complex 2 (x=1) on reaction with excess 1 affords mononuclear ReIII(OPPh2 (CH2)P(O)Ph2)Cl3(dppz), 4 while for x= 2-4 binuclear complex (dppz)Cl3ReIII(OPPh2 (CH2)xPPh2O)ReIIICl3 (dppz), 5 was obtained. Rate studies of the twin isomerization (linkage-cum-geometrical) reaction 2→3 revealed that the reaction is intramolecular in nature. It is initiated by the nucleophilic attack of the metal by the dangling phosphine function. The process slows down nearly exponentially as the diphosphine spacer length x increases. The oxidized complex [ReIV(OPPh2 (CH2)PPh2)Cl3 (dppz)]ReO4, 6 does not isomerize.

    Keywords

    Oxygen atom transfer, Twin isomerization, Pyridylpyridazine, Rhenium

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