Trans-philicity (trans-influence/trans-effect) ladders for square planar platinum(II) complexes constructed by 35 Cl NMR probe.
Athanassios C TsipisPublished in: Journal of computational chemistry (2019)
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(NH3 )2 (Cl)L and trans-Pt(CO)2 (Cl)L complexes employing 35 Cl NMR probe and quantified by calculation of NMR trans-philicity indicators. The trans-philicity is linearly correlated with the ligand electronic PL 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 σcalcd 35 Cl shielding constants, with the polar Dimethylformamide (DMF) solvent inducing downfield shifts relative to σcalcd 35 Cl with nonpolar benzene solvent. Good correlations between σcalcd 35 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.