The course aims to provide the basis for understanding the properties of the Metal-Carbon bond. The structural and spectroscopic characteristics of the metallorganic complexes are discussed. The mechanisms of the main reactions are examined: ligand substitution, oxidative addition / reductive elimination, insertion, binding to ligands. Therefore, some uses of the metallorganic compounds are illustrated as catalysts in organic synthesis and in industrial processes, in particular in polymerization reactions. During the course the students will learn to use quantum mechanics calculation programs to predict the properties of the compounds and their reactivity. It is expected that at the end of the course the student will be able to evaluate which structural features can have a metal-binding interaction, what is the potential reactivity of a specific metallorganic complex, which are the reactions that can produce a certain compound starting from a specific substrate.
Course Prerequisites
Molecular Orbital theory, symmetry, reaction mechanisms
Teaching Methods
Frontal lessons, individual and team exercises of computational chemistry
Assessment Methods
Exercises. At the end of the course there will be an oral exam where the student will prepare a presentation on an application of the methods of calculation acquired to apply them to the study of compounds and / or reactions treated during the course.
Texts
Didactic material given by teacher
Contents
Coordination chemistry (donor-acceptor, crystalline field theory, binder field, coordination geometry, chelation, metal complex magnetism, trans effect and influence). Binding-metal donation concept and metal-binding retrodonation (sigma-donor binders) , sigma-donors / pigreca-acceptors, pigreca-acceptors / pigreca-donors). Rule of 18-electrons, coordinated complexes saturated or unsaturated. Chemistry of organolithium compounds, organomagnesium, organoaluminum, organosilicon, organophosphorus. Systematic study of the main classes of metallorganic ligands. Alpha-agostic interactions, alpha-elimination, beta-elimination.Replacement reactions in octahedral and square planar complexes; dissociative mechanism, associative interchange, dissociative interchange, dissociative. Nucleophilic and electrophilic addition reactions to coordinated binders. Metallorganic catalysis. Role of the metallorganic catalyst.
