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Reactivity of nickel (II) diphosphine complexes towards alkoxides: A new route to the synthesis of nickel(0) compounds through nickel(II) alkoxides

Journal of the Chemical Society, Dalton Transactions, ISSN: 1472-7773, Issue: 19, Page: 2761-2764
1994
  • 27
    Citations
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  • 10
    Captures
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Metric Options:   Counts1 Year3 Year

Metrics Details

  • Citations
    27
    • Citation Indexes
      27
  • Captures
    10

Article Description

Reaction of [Ni(L-L)Cl] [L-L = PhP(CH)PPh, n = 2(dppe) or 3 (dppp)] with NaOR (R = Me, Et or Pr) under a dinitrogen atmosphere afforded [Ni(L-L)], Ni(OR) and aldehyde (or acetone when R = Pr) in 1: 1: 1 ratio, showing the peculiar reducing effect of alkoxide promoted by the chelating property of the phosphorus ligand. The reaction of NaOMe with [Ni(dcpe)Cl] [dcpe = 1,2-bis(dicyclohexylphosphino)-ethane] afforded mainly [Ni(dcpe)] when carried out in the absence of free diphosphine, and [Ni(dcpe)] in the presence of free diphosphine. The reaction always yields the nickel(0) species [Ni(L-L) (CO)] when it is carried out under a carbon monoxide atmosphere. The intermediate formation of unstable alkoxo(diphosphine)nickel(II) complexes has been demonstrated by recording the P NMR spectra of the reacting solutions at low temperature; in the case of the reaction of [Ni(dcpe)Cl] with NaOMe only, it was possible to isolate as a solid the [Ni(dcpe)(OMe)] complex, which has been fully characterized by analytical and spectroscopic (IR and H, P NMR) methods. A possible route by which nickel(0) complexes could be formed is discussed.

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