Ligand dependent topology and spontaneous resolution in high-spin cyano-bridged Ni3W2 clusters
| Autor: | Tadeusz Wasiutyński, Mateusz Reczyński, Wojciech Nitek, Beata Nowicka, Michał Rams, Barbara Sieklucka |
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| Rok vydání: | 2016 |
| Předmět: |
Denticity
Spin states 010405 organic chemistry Chemistry Stereochemistry Ligand 010402 general chemistry Topology 01 natural sciences 0104 chemical sciences Inorganic Chemistry Trigonal bipyramidal molecular geometry Bipyridine chemistry.chemical_compound Crystallography Cluster (physics) Enantiomer Diimine |
| Zdroj: | Dalton transactions (Cambridge, England : 2003). 45(31) |
| ISSN: | 1477-9234 |
| Popis: | Two high-spin pentanuclear NiW 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. 1Δ and 1Λ 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 P1[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. |
| Databáze: | OpenAIRE |
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