Trans-philicity (trans-influence/trans-effect) ladders for square planar platinum(II) complexes constructed by 35 Cl NMR probe

Athanassios C Tsipis

doi:10.1002/jcc.26031

Trans-philicity (trans-influence/trans-effect) ladders for square planar platinum(II) complexes constructed by ³⁵ Cl NMR probe

J Comput Chem. 2019 Nov 5;40(29):2550-2562. doi: 10.1002/jcc.26031. Epub 2019 Jul 13.

Author

Athanassios C Tsipis¹

Affiliation

¹ Laboratory of Inorganic and General Chemistry, University of Ioannina, 45110, Ioannina, Greece.

PMID: 31301188
DOI: 10.1002/jcc.26031

Abstract

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 P_L 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_calcd ³⁵ Cl shielding constants, with the polar Dimethylformamide (DMF) solvent inducing downfield shifts relative to σ_calcd ³⁵ Cl with nonpolar benzene solvent. Good correlations between σ_calcd 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.

Keywords: NMR trans-philicity ladders; ligand electronic parameters; square planar Pt(II) complexes; trans-effect ladders; trans-influence ladders; trans-philicity descriptors.