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Issue 4, 1983
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Crown ethers as second-sphere ligands. The interactions of transition-metal ammines with 18-crown-6 and dibenzo-18-crown-6

Abstract

Neutral and cationic transition-metal ammines interact with crown ethers in aqueous and non-aqueous solution via(N–H ⋯ O) hydrogen-bond formation to give discrete or polymeric adducts which are readily isolated by crystallisation. Dibenzo-18-crown-6 generally yields discrete 1 : 1 (metal complex : crown) adducts in which only one face of the macrocycle interacts with an ammine ligand, whereas 18-crown-6 often binds two such ligands, one to each face of the crown ether. The resulting adducts are then either polymeric or of 2 : 1 (metal complex : crown) stoicheiometry. Ammines which yield isolable adducts include [W(CO)5(NH3)], trans-[PtCl2(PMe3)(NH3)], trans-[PtCl2(NH3)2], [Co(NH3)6][PF6]3, [Cu(NH3)4(H2O)][PF6]2, and [Pt(H2NCH2CH2NH2)2][PF6]2. Such adduct formation provides the basis for a novel method of separating different transition metals; for example, 18-crown-6 selectively precipitates the copper(II) complex (as a polymeric 1:1 adduct) in the presence of an equimolar amount of the cobalt(III) ammine.

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Article type: Paper
DOI: 10.1039/DT9830000607
Citation: J. Chem. Soc., Dalton Trans., 1983,0, 607-613
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    Crown ethers as second-sphere ligands. The interactions of transition-metal ammines with 18-crown-6 and dibenzo-18-crown-6

    H. M. Colquhoun, D. F. Lewis, J. F. Stoddart and D. J. Williams, J. Chem. Soc., Dalton Trans., 1983, 0, 607
    DOI: 10.1039/DT9830000607

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