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Inorganic Grignard Analogues. Reaction of Nickel Powder with Dihalogenotriorganophosphorus Compounds to form Nickel-(II) and -(III) Phosphine Complexes; Isolation of Planar (1-) and the crystal Structure of

DOI: 10.1039/DT9930002875

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 2875 - 2882 (1993)

Update date:2022-08-03

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Authors:

Godfrey, Stephen M.Godfrey, Stephen M.

McAuliffe, Charles A.McAuliffe, Charles A.

Pritchard, Robin G.Pritchard, Robin G.

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Article abstract of DOI:10.1039/DT9930002875

Reactions of dihalogenotriorganophosphorus R3PX2 (X = Br or I) with unactivated coarsegrain nickel powder have been investigated.The nature of the nickel phosphine complexes formed is remarkably dependent on both R and X.Where R <*> Me and X = I the nickel(II) complexes are formed, analogous to, but not isostructural with, similar cobalt complexes of the same stoichiometry formed from cobalt powder and R3PI2.Quantitative electronic spectroscopic studies indicated that, surprisingly, the complexes all have predominantly square-planar geometry around nickel.Where R = Me and X = I, the nickel(III) complex is obtained in quantitative yield, the other product being diiodine.Reaction of nickel powder with Me2PhPI2 yields both the nickel(II) complex, , and the nickel(III) complex, .These observations again mirror analogous cobalt reactions.Reaction of the analogous dibromo compounds, R3PBr2, with nickel powder is extremely sensitive to the nature of R.Where R = Me, Et or Pnn no reaction occurs; where R3 = PhMe2 the square-planar complex and an octahedral complex of stoichiometry Ni(PPhMe2)2Br4 are obtained in equal yield.Where R3 = Ph2Prn the octahedral complex n)2Br4> is formed with a trace of the planar complex n)2Br2>, and where R = Ph the octahedral complex is formed in quantitative yield.The complex has been crystallographically characterised: monoclinic, space group P21/a, a = 10.018(2), b = 10.249(1), c = 10.138(1) Angstroem and Z = 2 (molecule centrosymmetric).

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Product name:{(CH3)2(C6H5)PI}(1+)*{Ni(P(CH3)2(C6H5))I3}(1-)={(CH3)2(C6H5)PI}{Ni(P(CH3)2(C6H5))I3}

Cas No:152386-21-5

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