Co-ordination chemistry of mixed pyridine–phenol ligands: polynuclear complexes of 6-(2-hydroxyphenyl)-2,2′-bipyridine with NiII, CdII, MnIIand MnIIMnIII
- 1 January 1995
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. 18,p. 3071-3080
- https://doi.org/10.1039/dt9950003071
Abstract
A series of complexes with the N,N,O-terdentate ligand 6-(2-hydroxyphenyl)-2,2′-bipyridine (HL1) has been prepared and structurally characterised. The complexes are [Ni2L1 2(dmf)2(H2O)2][BPh4]21(dmf = dimethylformamide), [Cd2L1 2(HL1)(dmf)2][BPh4]22, [Mn4L1 6][BPh4]23 and [Mn2L1 3(MeCN)][PF6]24. In the centrosymmetric complex 1 one ligand L1 is associated with each metal but the phenolates are bridging, giving a NiII 2(µ-O)2 core; the remaining two co-ordination sites are occupied by H2O and dmf (O-co-ordinated) ligands. In complex 2 one CdII ion is octahedrally co-ordinated by two ligands L1; the two phenolates bridge to the second CdII, whose co-ordination sphere is completed by two dmf ligands and the two pyridyl donors of another equivalent of HL1, whose pendant phenol remains protonated and forms hydrogen-bonding interactions to lattice solvent molecules. Complex 3 in contrast is an unusual example of a linear chain, with a MnII(µ-O)2MnII(µ-O)2MnII(µ-O)2MnII core (where O denotes a bridging phenolate) and highly distorted six-co-ordinate MnII centres: the chain formation is apparently facilitated by the absence of any stereoelectronic preference for the MnII ions which can readily tolerate the distorted geometries. Complex 4 contains a MnII centre, co-ordinated by two ligands L1, and a MnIII centre which shares two phenolates with the MnII and also has a terdentate L1 and a MeCN ligand to complete the co-ordination sphere. The MnIII centre shows Jahn–Teller elongation along one of the axes. The contributions of factors such as the metal oxidation state, the co-ordination modes available to the ligand, and non-covalent interactions (hydrogen bonding, aromatic π-stacking) to the structures of the complexes are discussed.Keywords
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