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Scandium Complexes Bearing Bis(oxazolinylphenyl)amide Ligands: An Analysis of Their Reactivity, Solution‐State Structures and Photophysical Properties
Author(s) -
Bennett Stacey D.,
Pope Simon J. A.,
Jenkins Robert L.,
Ward Benjamin D.
Publication year - 2016
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201600223
Subject(s) - chemistry , protonation , ligand (biochemistry) , steric effects , amide , scandium , salt metathesis reaction , reactivity (psychology) , medicinal chemistry , stereochemistry , luminescence , chloride , metathesis , organic chemistry , polymerization , medicine , ion , biochemistry , physics , receptor , alternative medicine , optoelectronics , pathology , polymer
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(SiMe 3 ) 2 } 2 ], but reaction of the protio‐ligand with [Sc{N(SiMe 3 ) 2 } 2 Cl(THF)] ( 1 ) afforded the mixed amido‐chloride complexes [Sc(R‐BOPA){N(SiMe 3 ) 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(SiMe 3 ) 2 ligand results in competitive protonation of the R‐BOPA ligand. The complexes [Sc(R‐BOPA)(CH 2 SiMe 2 Ph) 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.