Based on that geometry, we employed the NBO and EDA NOCV methods to perform a quantitative comparison across the three generations of our sulfonium pincer ligands in terms of their electronic properties, along with an optimized model complex [7*] 3+ , representing a synthetically inaccessible putative Pt(MeCN) complex of ligand L1 (Table ). While the EDA NOCV revealed no significant differences between the three model complexes ([5*] 3+ , [6*] 3+ , and [7*] 3+ ) in terms of type and strength of L-M orbital interactions, it indicated that ligand L3 is the weakest σ-donor and the strongest π-acceptor in this series. As a result, a positive charge on the Pt atom found by NBO is slightly higher in [5*] 3+ (+0.421), than in its counterparts (+0.407 and +0.395 in [6*] 3+ and [7*] 3+ , respectively). Encouraged by these computational results, we proceeded to the catalytic studies, focusing on complex [5](BF4)3. This complex was selected since it shares the anions with the analogous sulfonium and thioether complexes we reported earlier ([6](BF4)3 and [8](BF4)2, Scheme 4a), and therefore is best suited for evaluating the catalytic efficiency of the thiatriptycenium-based ligand. For this we employed the same benchmark reaction and substrate (9) as studied with the 2nd generation sulfonium ligand before (Scheme 4b and Table ). Fig. . Ligand effect on the rate of Pt-catalyzed cycloisomerization of 2-ethynyl-1,1'binapthalene (9). The dashed lines highlight the difference in time required to achieve 50% conversion with the 2nd and 3rd generation ligands.