Abstract
Heterometallic rare earth transition metal compounds of dithioxalate (dto)2-, [NiII{(dto)LnIIITp2}2] (Ln = Y (1), Gd (2); Tp = hydrotris(pyrazol-1-yl)borate) were synthesised. The Lewis acidic rare earth ions are bound to the dioxolene and chemical reduction of 1 and 2 with cobaltocene yielded [CoCp2]+[NiII{(dto)LnIIITp2}2]˙- Ln = Y (3), Gd (4). The reduction is ligand-based and 3 and 4 are the first examples of both molecular and electronic structural characterisation of the dithiooxalato radical (dto)3˙-.
Highlights
The Lewis acidic rare earth ions are bound to the dioxolene and chemical reduction of 1 and 2 with cobaltocene yielded [CoCp2]+[NiII{(dto)LnIIITp2}2]− Ln = Y (3), Gd (4)
The utility of this ditopic ligand stems from the asymmetry of the two binding sites: mid-to-late transition metal ions bind preferentially to the soft sulfur-donor dithiolate, whereas Lewis acidic metal ions bind preferentially to the hard oxygendonor α-diketonate.[2]. This has led to the assembly of numerous mixed-metal oligomers and coordination polymers by combining hard and soft metal ions with a dithioxalate salt in a one-pot reaction.[3,4,5,6]. The majority of these studies have focussed on the structural topology of the metal ions, and the magnetic properties of the constituent metal ions linked by this ligand
We report the synthesis and characterisation of two heterometallic compounds [NiII{(dto)YIIITp2}2] (1) and [NiII{(dto)GdIIITp2}2] (2) (Tp = hydrotris( pyrazol-1-yl)borate), in which the α-diketonate site is occupied by Lewis acidic rare earth ions
Summary
Molecular and electronic structure of the dithiooxalato radical ligand stabilised by rare earth coordination† The Lewis acidic rare earth ions are bound to the dioxolene and chemical reduction of 1 and 2 with cobaltocene yielded [CoCp2]+[NiII{(dto)LnIIITp2}2]− Ln = Y (3), Gd (4). The reduction is ligand-based and 3 and 4 are the first examples of both molecular and electronic structural characterisation of the dithiooxalato radical (dto)3−.
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