Study of the orthometallation mechanism of phenanthrolines with triruthenium acetates

• Grant number: 24/16876-7
• Support Opportunities: Scholarships abroad - Research Internship - Doctorate (Direct)
• Start date: February 03, 2025
• End date: February 02, 2026
• Field of knowledge: Physical Sciences and Mathematics - Chemistry - Inorganic Chemistry
• Principal Investigator: Sofia Nikolaou
• Grantee: Nicolle Azevedo Portela dos Santos
• Supervisor: Burkhard Butschke
• Host Institution: Faculdade de Filosofia, Ciências e Letras de Ribeirão Preto (FFCLRP). Universidade de São Paulo (USP). Ribeirão Preto , SP, Brazil
• Institution abroad: University of Freiburg, Germany
• Associated to the scholarship: 21/14279-3 - Study of the orthometallation of phenanthrolines with trinuclear ruthenium acetates, BP.DD

Abstract

Cyclometallated complexes are compounds in which the central metal atom is coordinated by a heteroatom (e.g. N, O, P) and a carbon atom of an organic molecule, thus producing a cycle with a metal atom in the ring. Such compounds possess a rich chemistry, thus leading to potential catalysts and metallodrugs. Labile triruthenium acetates can participate in cyclometallation reactions, thus producing complexes with orthometallated bidentate ligands. The literature describes such compounds for biological purposes and as units within extended structures. The attached PhD project aims to produce novel triruthenium acetates bearing orthometallated phenanthrolines for biological purposes. Besides that goal, the main objective of this project is the investigation of the mechanistic details of the orthometallation reaction for different phenanthrolines at the complex [Ru3O(CH-3COO)6(isoquinoline)2(CH3OH)][PF6]. For that purpose, we envisage a cooperation with Dr. Burkhard Butschke during an internship at the Institute for Inorganic and Analytic Chemistry of the University of Freiburg. The institute provides the necessary infrastructure for this project, and Dr. Butschke has a broad knowledge of cyclometallation reactions and mechanistic studies in general. We propose to investigate both solution and gas-phase reactivity, using nuclear magnetic resonance spectroscopy (NMR spectroscopy), mass spectrometry (MS), and single-crystal X-ray diffraction (sc-XRD). The first technique will be used for time-resolved and variable-temperature experiments, the second for mixing experiments prior to ionization, for collision-induced dissociation experiments (CID experiments), and for isotope-labeling experiments. sc-XRD might help in the structural characterization of reaction intermediates. The results of this internship will be divulged in scientific events and articles.