| Full text | |
| Author(s): |
Oliveira, Pedro P. R.
;
Batista, Patrick R.
;
Ducati, Lucas C.
;
Autschbach, Jochen
Total Authors: 4
|
| Document type: | Journal article |
| Source: | Inorganic Chemistry; v. N/A, p. 8-pg., 2025-10-17. |
| Abstract | |
This study investigates the trans influence in dinuclear platinum(III) complexes using a combined approach of ab initio molecular dynamics and natural localized molecular orbital (NLMO) analysis. Focusing on pivalamidate-bridged PtIII complexes with axial ligands of varying sigma-donation strength, it is quantified how ligand-metal interactions propagate through the Pt-Pt bond, and how they affect bond polarization, axial water coordination, and 1 J PtPt spin-spin coupling constants. NLMO analysis reveals quantitatively that strong sigma-donating ligands polarize the Pt-Pt bond, shifting the electron density toward the opposite platinum center. The polarization mechanism is identified as the primary reason for the observed reduction of 1 J PtPt, because the bond polarization diminishes the transmission of the nuclear magnetic spin-induced electron spin density through the Pt-Pt bond. Additionally, the destabilization of axial water coordination at the opposite Pt site can be rationalized through a polarization-induced PtIV- PtII-like mixed-valence character. (AU) | |
| FAPESP's process: | 24/00633-8 - Probing the Kinetic Trans Effect in Halide Ion Substitution Reactions of Dinuclear Pt(III) Complexes Through Metadynamics Simulations |
| Grantee: | Pedro Paulo Rezende Oliveira |
| Support Opportunities: | Scholarships abroad - Research Internship - Master's degree |
| FAPESP's process: | 24/17236-1 - Solvent Effect on NMR Parameters of Tl(III) and Pt(IV) Complexes by ab initio Molecular Dynamics and Relativistic Calculations |
| Grantee: | Lucas Colucci Ducati |
| Support Opportunities: | Regular Research Grants |
| FAPESP's process: | 21/09687-5 - Assessment of conformational preferences on fluorine-containing molecules and study of transmission pathway for JFH couplings using Car-Parrinello molecular dynamics |
| Grantee: | Patrick Rodrigues Batista |
| Support Opportunities: | Scholarships in Brazil - Post-Doctoral |
| FAPESP's process: | 18/07308-4 - Effect of solvent on shielding tensor and coupling constant calculations of platinum (iii) dinuclear complexes via ab initio molecular dynamics |
| Grantee: | Patrick Rodrigues Batista |
| Support Opportunities: | Scholarships in Brazil - Doctorate |
| FAPESP's process: | 22/12004-0 - Ab Initio Investigation of the Solvent and Different Ligands on the 195Pt NMR Properties in Pt(III) Dinuclear Complexes |
| Grantee: | Pedro Paulo Rezende Oliveira |
| Support Opportunities: | Scholarships in Brazil - Master |