Work

Trans-Influence in Dinuclear Pt(III) Complexes: Electronic Structure, σ-Donation, and Pt–Pt Spin–Spin Coupling

Year: 2025

Type: article

Abstract: High Resolution Image Download MS PowerPoint Slide 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 Pt III 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 1 J PtPt 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 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 Pt IV – Pt II -like mixed-valence character.

Source: Inorganic Chemistry

DOI: 10.1021/acs.inorgchem.5c03401

Authors: Pedro P. R. Oliveira, Patrick R. Batista, Lucas C. Ducati, Jochen Autschbach

Institutions: Universidade de São Paulo, Institute of Chemistry, Viện Hóa học, University at Buffalo, State University of New York

Language: English

Topic: Inorganic and Organometallic Chemistry

Subfield: Organic Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: hybrid

Estimated APC paid: $4,500

Funders: Fundação de Amparo à Pesquisa do Estado de São Paulo, Coordenação de Aperfeiçoamento de Pessoal de Nível Superior, Conselho Nacional de Desenvolvimento Científico e Tecnológico, Basic Energy Sciences