Heteroleptic lanthanide(III) complexes: synthetic utility and versatility of the unsubstituted bis-scorpionate ligand framework

Chowdhury, T., Horsewill, S. J., Wilson, C. and Farnaby, J. H. (2022) Heteroleptic lanthanide(III) complexes: synthetic utility and versatility of the unsubstituted bis-scorpionate ligand framework. Australian Journal of Chemistry, 75(9), pp. 660-675. (doi: 10.1071/CH21313)

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Abstract

The unsubstituted bis-hydrotris(1-pyrazolyl)borate) (Tp) ligand framework has been used to synthesise a range of heteroleptic Ln(III) coordination complexes [Ln(Tp)2(X)]. The precursor complexes [Ln(Tp)2(OTf)] 1-Ln (Ln = Y, Eu, Gd, Yb; OTf = triflate) were synthesised by reaction of Ln(OTf)3 with two equivalents of K(Tp). The 8-coordinate β-diketonate complexes [Ln(Tp)2(hfac)] 2-Ln (Ln = Y, Eu, Yb; hfac = hexafluoroacetylacetonate) were synthesised from Ln(OTf)3 by reacting 1-Ln generated in situ with an equivalent of K(hfac). The 7-coordinate amide complexes [Ln(Tp)2(N″)] 3-Ln (Ln = Y, Yb; N″ = bis(trimethylsilyl)amide) were synthesised from 1-Ln by reaction with K(N″). Reactivity of 3-Ln towards protonolysis was demonstrated by the isolation of the hydroxide dimer [{Y(Tp)2(μ-OH)}2] 4-Y from adventitious reaction with water and the aryloxide complex [Ln(Tp)2(OAr)] 5-Ln (Ln = Y, Yb; OAr = 2,6-tBu2-4-Me-phenoxide) from reaction with H(OAr). Full characterisation data are presented for all complexes, including solid-state molecular structure determination by single-crystal X-ray diffraction.

Item Type:Articles
Status:Published
Refereed:Yes
Glasgow Author(s) Enlighten ID:Wilson, Dr Claire and Farnaby, Dr Joy and Horsewill, Samuel and Chowdhury, Mr Tajrian
Authors: Chowdhury, T., Horsewill, S. J., Wilson, C., and Farnaby, J. H.
College/School:College of Science and Engineering > School of Chemistry
Journal Name:Australian Journal of Chemistry
Publisher:CSIRO Publishing
ISSN:0004-9425
ISSN (Online):1445-0038
Published Online:03 April 2022

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Project CodeAward NoProject NamePrincipal InvestigatorFunder's NameFunder RefLead Dept
190906EPSRC 2015 DTPMary Beth KneafseyEngineering and Physical Sciences Research Council (EPSRC)EP/M508056/1Research and Innovation Services