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 σ^iso(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 σ^iso(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 σ^iso(SO) X NMR descriptors of trans-philicity linearly correlated with the ligand electronic P_L 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.