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Synthesis and characterisation of a chiral lanthanoid cluster with an unusually exposed cubane core via concomitant deesterification of ethyl acetate
Authors:Philip C AndrewsWilliam J Gee  Peter C Junk  Jonathan G MacLellan
Institution:School of Chemistry, Monash University, Victoria 3800, Australia
Abstract:An unusual chiral lanthanoid cluster has been synthesised and characterised that exhibits a cubane cage motif with a remarkably exposed central core. This discovery stems from the use of a new asymmetric diketone ligand, (Z)-3-hydroxy-3-methyl-1-(1,2:3,4-di-O-isopropylidene-α-d-galactopyranose)prop-2-en-1-one (Hmgp), which incorporates both a methyl terminus and a protected d-galactose moiety to induce chirality. Reaction of this ligand with hydrated holmium chloride results in the formation of a cubane cluster, Ho4(μ3-OH)4(η2-mgp)6(μ-η2-mgp)(μ-η2-Ac)(H2O)2] (1), which bears seven chiral ligands that form a highly shielded hemisphere and an acetate co-ligand that is postulated to form via deesterification of ethyl acetate.
Keywords:Lanthanoid  Rare earth  Chiral cluster  Cubane  Diketone  Carbohydrate  Deesterification
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