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Issue 9, 1988
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Sulfur–nitrogen bonded metal chelates. Part 17. Reactions of alcohols with the co-ordinated nitrile in nickel(II) complexes [NiL(NCR)][ClO4](L = a S,N,N-tridentate anion; R = Me, Et, or Ph) under different conditions

Abstract

The reactions of the nitrile complexes [NiL(NCR)][ClO4]{HL1= methyl 2-[(2′-aminoethyl)amino]-cyclopent-1-enedithiocarboxylate, HL2= methyl 2-[(2′-dimethylaminoethyl)amino]cyclopent-1-enedithiocarboxylate, HL3= methyl 2-[(2′-diethylaminoethyl)amino]cyclopent-1-enedithio-carboxylate; R = Me, Et, or Ph} with methanol and ethanol under different experimental conditions have been investigated. Rate constants for these reactions have been measured spectrophotometric ally at 25 °C. Dry methanol reacts with the nitrile complexes, in absence of free nitrile, to produce dinuclear µ-methoxo complexes [Ni2L2(µ-OMe)][ClO4] and the same reaction with wet methanol gives [Ni2L2(µ-OH)][ClO4]. Both methoxo- and hydroxo-bridged compounds react with imidazole to form µ-imidazolato dinuclear complexes. All the complexes have been isolated and characterized. Dry methanol adds to the co-ordinated nitrile in complexes [NiL(NCR)][ClO4] in the presence of excess of free RCN, to produce imino-ether complexes [NiL{NH[double bond, length half m-dash]C(OMe)R}][ClO4]. The rate data show the following decreasing order of reactivity of the nitrile complexes: [NiL1(NCMe)]+ > [NiL1(NCEt)]+ > [NiL2(NCMe)]+ > [NiL3(NCMe)]+. The reaction rate with ethanol is much slower than that with methanol. The rates of formation of imino-ether complexes increase by more than four orders of magnitude when sodium alkoxide is used as a catalyst.

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Article type: Paper
DOI: 10.1039/DT9880002373
J. Chem. Soc., Dalton Trans., 1988, 2373-2378

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    Sulfur–nitrogen bonded metal chelates. Part 17. Reactions of alcohols with the co-ordinated nitrile in nickel(II) complexes [NiL(NCR)][ClO4](L = a S,N,N-tridentate anion; R = Me, Et, or Ph) under different conditions

    P. Paul and K. Nag, J. Chem. Soc., Dalton Trans., 1988, 2373
    DOI: 10.1039/DT9880002373

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