Abstract
Quantifying the donor ability of bidentate ligands in inorganic chemistry is not straightforward, and the Huynh electronic parameter for chelators (HEP2) presents a rare solution to the task. Aiming to extend the ligand scope in this work, the soundness and practicality of HEP2 was further scrutinized with seven stereoelectronically diverse β-ketiminato ("NacAc") chelators using palladium complexes of the type [PdBr(iPr2-bimy)(ArNacAc)] (iPr2-bimy = 1,3-diisopropylbenzimidazolin-2-ylidene). Notably, the unsymmetrical nature of this κ2-N,O ligand family allowed for an intriguing exploration into isomerism in the square planar PdII products, which depends on the N-aryl ortho- and para-substituents based on experimental and theoretical findings. The HEP2 values of both isomeric forms correlate well with the widely used σp Hammett constants, which reinforces the reliability of this modern methodology.
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