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Updated: Jan 14, 2026
Amide Coupling Reaction for the Synthesis of Bispyridine-based Ligands and Their Complexation to Platinum as Dinuclear Anticancer Agents
Published on: May 28, 2014
Trans-Influence in Dinuclear Pt(III) Complexes: Electronic Structure, σ-Donation, and Pt-Pt Spin-Spin Coupling
Pedro P R Oliveira1, Patrick R Batista1, Lucas C Ducati1
1Department of Fundamental Chemistry, Institute of Chemistry, University of São Paulo, São Paulo, São Paulo 05508-000, Brazil.
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 σ-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 1JPtPt spin-spin coupling constants. NLMO analysis reveals quantitatively that strong σ-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 1JPtPt, 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.
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