NMR probe effects on: Trans-philicity and trans-influence ladders in square planar Pt(ii) complexes

Abstract

Quantitative trans-philicity ladders for a broad series of ligands in square planar trans-[Pt(PMe3)2(X)L]n (n = 0, 1, 2; X = H, CO, CH3, NH2, OH2, Cl) complexes are built employing the isotropic σiso(SO) X NMR shielding constants, calculated by DFT computational protocols at the SO-ZORA level of theory, as the trans-philicity descriptors. Linear relationships between the σiso(SO) X trans-philicity descriptors and the R(Pt-X) descriptors of trans-influence demonstrate the relation of trans-philicity with trans-influence. The electronic features of the probes are crucial factors that manipulate trans-philicity. The isotropic σiso(SO) X NMR descriptors of trans-philicity linearly correlated with the ligand electronic PL constants and other popular electronic/structural descriptors related with the L-Pt-X bonding, revealed the origin of trans philicity. The trans-philicity ladders constructed by the six different probes go roughly parallel with only minor deviations related with the position of L in the rungs of the ladders.