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Issue 31, 2016
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Ligand dependent topology and spontaneous resolution in high-spin cyano-bridged Ni3W2 clusters

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Abstract

Two high-spin pentanuclear NiII3WV2 clusters with diimine blocking ligands have been obtained: {[Ni(4,4′-MeObpy)2]3[W(CN)8]2}·12H2O (1) and {[Ni(phen)2(H2O)][Ni(phen)2]2[W(CN)8]2}·7H2O (2) (4,4′-MeObpy = 4,4′-dimethoxy-2,2′-bipyridine, phen = 1,10-phenanthroline). Despite the similarity of the building blocks and synthetic conditions the compounds show different topologies of the cluster core: 1 is a trigonal bipyramid while 2 is a decorated square. Both cluster structures are chiral with either ΔΔΔ or ΛΛΛ configuration around all three Ni centres. In 1 spontaneous resolution occurs and it crystallises in the P212121 space group forming a conglomerate containing both types of enantiomorphic crystals. and are the first pair of enantiomorphic structures of cyano-bridged clusters of trigonal bipyramidal topology obtained with achiral bidentate blocking ligands. 2 crystallises as a racemic compound in a centrosymmetric space group P[1 with combining macron] with both enantiomers present in the structure. 2 is an exceptional square-motif containing structure with an identical stereoconfiguration of all complex cations within one cluster. Ferromagnetic interactions are present in both clusters resulting in the ground spin state S = 4.

Graphical abstract: Ligand dependent topology and spontaneous resolution in high-spin cyano-bridged Ni3W2 clusters

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Publication details

The article was received on 26 May 2016, accepted on 04 Jul 2016 and first published on 05 Jul 2016


Article type: Paper
DOI: 10.1039/C6DT02119K
Citation: Dalton Trans., 2016,45, 12423-12431

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    Ligand dependent topology and spontaneous resolution in high-spin cyano-bridged Ni3W2 clusters

    B. Nowicka, M. Reczyński, M. Rams, T. Wasiutyński, W. Nitek and B. Sieklucka, Dalton Trans., 2016, 45, 12423
    DOI: 10.1039/C6DT02119K

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