27232 - Homogeneous Catalysis
Optional
5.1. Methodological overview
The methodology followed in this course is oriented towards achievement of the learning objectives. It favors the understanding of the different chemical processes that occur in homogeneous catalysis as well as an overview about industrial processes based on transition metal homogeneous catalysts. A wide range of teaching and learning tasks are implemented, such as theory sessions and tutorials.
Students are expected to participate actively in the class throughout the semester.
Classroom materials will be available via Moodle. These include a repository of the lecture notes used in class, the course syllabus, as well as other course-specific learning materials.
Further information regarding the course will be provided on the first day of class.
5.3. Syllabus
The course will address the following topics:
Theory sessions
Section 1. Introduction
Topic 1. Introduction to homogeneous catalysis
Basic concepts and importance of homogeneous catalysis. Green-Chemistry and catalysis. The selectivity of a catalytic process. Transition metal compounds and their application as homogeneous catalysts. The 18-electron rule. The electronic and steric effects exerted by the ligands in transition metal complexes. Coordinative unsaturation. Trans effect and trans influence.
Topic 2.Fundamental Reactions in Homogeneous Catalysis
Oxidative addition and reductive elimination reactions Characteristics of the oxidative addition reactions. Classification of the oxidative addition reactions. Mechanisms of the oxidative addition reactions. Oxidative addition of C-H bonds to transition metal complexes. Characteristics of the reductive elimination reactions and some examples. Insertion and elimination reactions. Reactions involving attack to coordinated ligands. Characteristics of the insertion and elimination reactions. Mechanisms of the insertion reactions. Characteristics of the alpha and beta elimination reactions. Changes in the reactivity of coordinated ligands. Examples of reactions involving attack to coordinated ligands.
Section 2. Applications of the homogenous catalysis
Topic 1. Isomerization
Isomerization of alkenes: positional isomerization, cis-trans isomerization, skeletal isomerization. Asymmetric Isomerization: synthesis of menthol.
Topic 2. Hydrogenation
Hydrogen activation. Homogeneous hydrogenation mechanisms. Representative hydrogenation catalysts. Asymmetric Hydrogenation. Non-classics mechanisms: bifunctional, ionic. Hydrogen transfer reactions.
Topic 3. Carbonylation
Characteristics of the carbonylation reactions. Carbonylation of methanol. Carbonylation of methyl acetate. Hydroformylation. Copolymerization of carbon monoxide and olefins.
Topic 4. Oxidation
Characteristics of the oxidation reactions. The Wacker process. Epoxidation of olefins. Oxidation of C-H bonds. Polymerization and oligomerization.
Topic 5. Olefin polymerization.
Representative catalysts for olefin polymerization: Ziegler-Natta catalysts, metallocenes, other catalysts. Mechanism of polymerization reactions. Polymers and copolymers. Dimerization and oligomerization. SHOP process (Shell Higher Olefin Process).
Topic 6. Metathesis
Metathesis reactions. Metathesis of acyclic and cyclic olefins. Mechanism of reactions of olefin metathesis. Types of metathesis catalysts. Applications of the metathesis reactions.
Topic 7. Hydrocyanation and hydrosilylation
Characteristics of the hydrocyanation reactions. Preparation of adiponitrile by hydrocyanation of butadiene. Characteristics of the hydrosilylation reactions. Mechanisms of the hydrosilylation reactions.
Topic 8. Carbon-carbon coupling reactions
Carbon-carbon coupling reactions: Heck reaction, carbon-carbon coupling reactions via transmetallation. Other C-C coupling reactions.