Binding a meridional ligand in a facial geometry: A square peg in a round hole

• Published in: Journal of organometallic chemistry Vol. 919; p. 121331
• Main Authors: Schrage, Briana R., Vitale, Dominick, Kelly, Kimberly A., Nemykin, Victor N., Herrick, Richard S., Ziegler, Christopher J.
• Format: Journal Article
• Language: English
• Published: Switzerland Elsevier B.V 15-07-2020
• Subjects: Bis(pyridylimino)isoindoline; DFT/TDDFT calculations; Rhenium tricarbonyl; Transition metal geometry; X-ray crystallography; X-ray crystallography; Rhenium tricarbonyl; Transition metal geometry; DFT/TDDFT calculations; Bis(pyridylimino)isoindoline
• ISSN: 0022-328X; 1872-8561
• DOI: 10.1016/j.jorganchem.2020.121331

The bis(pyridylimino)isoindoline (BPI) ligand is a tridentate chelate that binds to metals via a meridional coordination mode. However, when this ligand forms a complex with Re(CO)3, an almost exclusively facial moiety, the BPI ligand deforms to coordinate in a facial mode. We have investigated this deformation via structural and theoretical means, and the non-planar binding mode of the ligand bathochromically shifts the metal to ligand charge transfer (MLCT) transition.
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•The bis(pyridylimino)isoindoline (BPI) ligand, coordinates to Re(CO)3 in a facial mode.•The BPI ligand undergoes significant distortion from planarity.•These compounds exhibit MLCT bands in their UV–visible spectra.