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Scandium complexes bearing bis(oxazolinylphenyl)amide ligands: an analysis of their reactivity, solution-state structures and photophysical properties

Bennett, Stacey D., Pope, Simon J. A., Jenkins, Robert Leyshon and Ward, Benjamin D. 2016. Scandium complexes bearing bis(oxazolinylphenyl)amide ligands: an analysis of their reactivity, solution-state structures and photophysical properties. European Journal of Inorganic Chemistry 2016 (18) , pp. 2932-2941. 10.1002/ejic.201600223

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Abstract

The coordination chemistry of scandium supported by bis(oxazolinylphenyl)amide (R-BOPA) ligands is reported. The R-BOPA ligand is too sterically demanding to afford bis(amide) complexes [Sc(R-BOPA){N(SiMe3)2}2], but reaction of the protio-ligand with [Sc{N(SiMe3)2}2Cl(THF)] (1) afforded the mixed amido-chloride complexes [Sc(R-BOPA){N(SiMe3)2}Cl] (2). The selective reaction of the amido and chloride co-ligands in 2 has been investigated; whilst the chloride ligand can be removed cleanly by metathesis, protonation of the N(SiMe3)2 ligand results in competitive protonation of the R-BOPA ligand. The complexes [Sc(R-BOPA)(CH2SiMe2Ph)2] (5) have been synthesised. Each R-BOPA-containing complex exists in two isomeric forms. The equilibrium has been investigated both experimentally and computationally, and the data suggest that a concerted rotation of the phenyl rings interconverts the two diastereomeric isomers. All of the R-BOPA complexes were found to be luminescent; an analysis of the photophysics, aided by TD-DFT calculations, suggests ligand-centred luminescence with distinct emission lifetimes for each isomer.

Item Type: Article
Date Type: Published Online
Status: Published
Schools: Advanced Research Computing @ Cardiff (ARCCA)
Chemistry
Subjects: Q Science > QD Chemistry
Additional Information: PDF uploaded in accordance with publisher's policies at http://www.sherpa.ac.uk/romeo/issn/1434-1948/ (accessed 3.6.16).
Publisher: Wiley
ISSN: 1434-1948
Funders: EPSRC
Date of First Compliant Deposit: 3 June 2016
Date of Acceptance: 2 March 2016
Last Modified: 22 Feb 2019 22:26
URI: http://orca.cf.ac.uk/id/eprint/91321

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