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Trans ‐philicity ( trans ‐influence/ trans ‐effect) ladders for square planar platinum(II) complexes constructed by 35 Cl NMR probe
Author(s) -
Tsipis Athanassios C.
Publication year - 2019
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.26031
Subject(s) - chemistry , cis–trans isomerism , ligand (biochemistry) , solvent effects , solvent , chemical shift , trans effect , computational chemistry , crystallography , stereochemistry , molecule , organic chemistry , biochemistry , receptor
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 3 ) 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.