Trans-philicity (trans-influence/trans-effect) ladders for square planar platinum(II) complexes constructed by Cl NMR probe.

The unified term of trans-philicity is proposed to cover the trans-effect/trans-influence concepts. NMR trans-philicity ladders are built for a broad series of square planar trans-Pt(NH ) (Cl)L and trans-Pt(CO) (Cl)L complexes employing Cl NMR probe and quantified by calculation of NMR trans-philicity indicators. The trans-philicity is linearly correlated with the ligand electronic P constant, a measure of the net donor power of the ligand. The nature of cis-ligands does not affect trans-philicity ladders but strongly affects trans-philicity strength. Solvent has significant effect on the σ Cl shielding constants, with the polar Dimethylformamide (DMF) solvent inducing downfield shifts relative to σ Cl with nonpolar benzene solvent. Good correlations between σ Cl shielding constants and the estimated R(Pt-Cl) bond distances demonstrate the relation of trans-philicity with trans-influence and trans-effect phenomena and put the grounds for the establishment of the new concept of trans-philicity in the realm of square planar Pt(II) and other transition metal complexes. © 2019 Wiley Periodicals, Inc.