Synthesis and characterization of nickel(II) phosphonate complexes utilizing pyridonates and carboxylates as co-ligands

Stuart K Langley; Madeleine Helliwell; Simon J Teat; Richard E P Winpenny

doi:10.1021/ic4026816

Synthesis and characterization of nickel(II) phosphonate complexes utilizing pyridonates and carboxylates as co-ligands

Inorg Chem. 2014 Jan 21;53(2):1128-34. doi: 10.1021/ic4026816. Epub 2014 Jan 6.

Authors

Stuart K Langley¹, Madeleine Helliwell, Simon J Teat, Richard E P Winpenny

Affiliation

¹ School of Chemistry and §The Photon Science Institute, The University of Manchester , Oxford Road, Manchester, M13 9PL, U.K.

PMID: 24392684
DOI: 10.1021/ic4026816

Abstract

The synthesis and structures of five new nickel complexes containing phosphonate ligands are reported. The compounds utilize pivalic acid (HPiv) and 6-chloro-2-pyridonate (Hchp) as co-ligands with the resulting complexes being of formulas [Ni10(chp)4(Hchp)4.5(O3P(t)Bu)3(Piv)5(HPiv)2(OH)6(H2O)4.5](HNEt3)·0.5MeCN·2.5H2O 1, [Ni12(chp)12(Hchp)2(PhPO3)2(Piv)5(HPiv)2(OH)2(H2O)6](F)·4.5MeCN·2H2O 2, [Ni10(chp)6(O3PCH2Ph)2(Piv)8(F)2(MeCN)4] 3, [Ni10(chp)6(O3PMe)2(Piv)8(F)2 (MeCN)4]·5MeCN·2H2O 4, and [Ni10(chp)6(O3PCH2Nap)2(Piv)8(F)2(MeCN)2(H2O)2] 5. The metallic core of compounds 1 and 2 display tetra- and hexa-capped trigonal prismatic arrangements, while the metallic and phosphorus core of 3, 4, and 5 display three face-sharing octahedra. Variable temperature direct current (dc) magnetic susceptibility measurements reveal dominant antiferromagnetic exchange interactions within each cluster, with diamagnetic spin ground states found.