Canty, Allan J.Ariafard, Alirezavan Koten, Gerard2026-01-012026-01-010947-6539PubMed:32696509ORCID:/0000-0003-2383-6380/work/198195234https://hdl.handle.net/1885/733800863Density Functional Theory studies of square-planar PtII pincer structures, (4-Z-NCN)PtCl ([4-Z-NCN]−=[4-Z-2,6-(Me2NCH2)2C6H2-N,C,N]−, Z=H, NO2, CF3, CO2H, CHO, Cl, Br, I, F, SMe, SiMe3, tBu, OH, NH2, NMe2), enable characterisation of mesomerism for the pincer-Pt interaction. Relationships between Hammett σp substituent parameters of Z and DFT data obtained from NBO6 and AOMix computation are used to probe the interaction of the 5dyz orbital of platinum with π-orbitals of the arene ring. Analogous computation for 2,6-(Me2CH2)2C6H3Z (Z=H, CF3, CHO, Cl, Br, I, F, SMe, SiMe3, tBu, OH, NH2) and (4-H-NCN)PtZ allows an estimation of the relative substituent effects of “(CH2NMe2)2PtZ” on π-delocalisation in the pincer system.This work was supported by the Australian Research Council, the Australian National Computing Infrastructure and The University of Tasmania.7en© 2020 The Authorsdensity functional calculationsHammettorganoplatinumpincersubstituent effects2020-12-0110.1002/chem.20200302385092731878