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

<p>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] (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.    The dataset contains all experimental spectroscopic data (e.g. NMR data), crystallographic data (raw hl files), and computational output (Gaussian format).<br><br>Research results based upon these data are published at http://dx.doi.org/10.1002/ejic.201600223<br></p>