Scholarship 22/12004-0 - Teoria do funcional da densidade, Ressonância magnética nuclear - BV FAPESP
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Ab Initio Investigation of the Solvent and Different Ligands on the 195Pt NMR Properties in Pt(III) Dinuclear Complexes

Grant number: 22/12004-0
Support Opportunities:Scholarships in Brazil - Master
Start date until: March 01, 2023
End date until: August 31, 2025
Field of knowledge:Physical Sciences and Mathematics - Chemistry - Physical-Chemistry
Principal Investigator:Lucas Colucci Ducati
Grantee:Pedro Paulo Rezende Oliveira
Host Institution: Instituto de Química (IQ). Universidade de São Paulo (USP). São Paulo , SP, Brazil
Associated scholarship(s):24/00633-8 - Probing the Kinetic Trans Effect in Halide Ion Substitution Reactions of Dinuclear Pt(III) Complexes Through Metadynamics Simulations, BE.EP.MS

Abstract

Dinuclear platinum complexes play a fundamental role in many of nature's processes, including,for example, photochemistry and catalysis. Nevertheless, to understand the NMR parametertrends of the 195Pt nucleus in solution poses challenges, requiring a high computational leveltaking account the relativistic effects. Moreover, theoretical studies report that the use of explicit solvation and the description of the solute-solvent system in a dynamic way is imperative to improve the accuracy of the calculated 195Pt spin-spin coupling constants (J-coupling) and chemical shifts. Pt(III)-containing complexes are very rare and characterized by apolymeric/oligomeric structure involving bonds between two d7 Pt atoms, and their NMR data isworthy of particular attention. These complexes are in equilibrium in an aqueous media and maypresent the cis/trans influence in solution, where the Pt-Pt bond lengthens with increasing axialligand sigma-donor strength. Given the challenges of understanding the 195Pt NMR trends, an ab initio investigation is proposed in this project, concerning to modeling the explicit solvent-soluteinteractions and the way coordinating ligands affect the structural parameters, electronic structure, J-coupling and chemical shifts of a series of pivalamidate-bridged Pt(III) dinuclear complexes. The selected Pt-Pt bonded systems are interesting in terms of their potential applications, and present a very challenging test case to see how far the theoretical methods can be pushed at present. For this, the better realistic theoretical method combining the Car-Parrinello molecular dynamics and relativistic hybrid Kohn-Sham Density Functional NMR calculations will be applied.

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