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

Howard M. Colquhoun*, David F. Lewis, J. Fraser Stoddart, David J. Williams

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

76 Scopus citations

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.

Original languageEnglish (US)
Pages (from-to)607-613
Number of pages7
JournalJournal of the Chemical Society, Dalton Transactions
Issue number4
DOIs
StatePublished - 1983

ASJC Scopus subject areas

  • Chemistry(all)

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