Organometallic Chemistry and Catalysis

Teaching Methods

Teachers should approach the subjects using up-to-date information and taking advantage of their experience as researchers within this field. The curricular unit - Organometallic Chemistry and Catalysis - in addition to theoretical classes comprises theoretical-practical classes in which students will solve problems and discuss themes and seminars in which students will present short research assignments they have developed individually, covering the topics that were approached in theoretical classes.

Participation of students in classes will be encouraged since interactivity will provide them with a greater motivation and will be an important indicator for teachers to know if students are or are not following the approached subjects.

Audio-visual media will be used simultaneously with the board. This is an important tool for the discussion of some themes because the rhythm of the subjects’ presentation allows students to follow them better.

Students are expected to make an effort to self-learn but this self-learning may be partially guided by tutorial sessions.

Visits to Industrial Units where catalytic systems are applied in production processes either in the field of Petrochemistry or the field of Pharmaceutical and Food Chemistry.

Students will attend demonstration classes in a research laboratory of synthesis techniques of organometallic compounds in an inert atmosphere and their application in catalytic processes in order to contribute to a greater motivation and understanding of the approached subjects.

Learning Outcomes

1. Knowledge and ability to understand:

1.1. Understand concepts and basic principles of organometallic synthesis and reactivity.

1.2. Ability to analyse, summarize and understand manipulation and synthesis processes involving organometallic compounds.

2. Application of knowledge and understanding:

2.1. Know how to apply the acquired knowledge applying it in the specific vocational field in terms of the professional approach, namely the development and use of catalysts in industry.

3. Accomplishment of judgements/ decision making:

3.1. Ability to solve problems within the field of catalysis in larger-scale processes.

3.2. Know how to substantiate a personal argumentation while making decisions.

3.3. Decide which the best strategy in catalytic processes is, having in mind catalyst’s cost, its stability and environmental issues.

4. Communication:

4.1. Understand and know how to use information sources. Ability to do research and use the bibliography.

4.2. Have acquired competences that allow students to convey information in a clear way and using appropriate speech and media. Have acquired skills in the structured presentation of scientific subjects to a competent audience and ability to argue either in writing or orally. Have knowledge of the problem that is associated with the increase in the reaction scale.

5. Self-learning competences:

5.1. Acquire competences that allow students to carry out lifelong self-learning.

5.2. Acquire competences to decide which the best strategy is to carry out a chemical synthesis of an unknown compound using organometallic compounds.

Work Placement(s)

No

Syllabus

Organoalkaline reagentes:

Organomagnesium Reagents and Organoleptic compounds – manipulation synthesis and industrial applications.

Types of connections in organometallic compounds of transition metals:

Metal carbonyl, olefin and phosphine. Compounds of the type Metallocene and arenum. Synthesis and stability of organometallic complexes. Heptacity. The 18 electron rule.

Properties and characterization and main reactions of the transition metal complexes.

Substitution, oxidative addition, insertion, elimination, isomerization and reductive elimination.

Phosphorus Ligands synthesis and their transition metals complexes.

Nuclear Magnetic Resonance Spectroscopy and infra-red Spectroscopy in the characterization of the organometallic compounds. Examples of application.

Homogeneous and Heterogeneous Catalysis:

The Catalysis phenomenon; action mode of a catalyst; classification of catalysts; principles of homogeneous catalysis; principles of heterogeneous catalysis; Kinetics of catalytic processes.

Homogeneous Catalysis Reaction with Industrial Applications.

Carbonylation reaction: Synthesis of Acetic Acid – Carbonylation of Methanol. Fundamentals of the reaction: catalytic mechanism and cycle. Synthesis reaction of Methyl methacrylate – Carbonylation of alkenes.

Metallocene Polymerization Catalysts. Reaction mechanisms of polymerization and stereochemical control. Polymerization reactions by means of metathesis of cyclic olefins. Palladium organometallic complexes in the formation of carbon-carbon connection.

Oxidation of Olefins:

Oxidations with metals involving free radicals.

Oxidations of the Ethylene Acetaldehyde: Wacker process.

Epoxidation of Olefins: phase transfer catalysts in oxidation reactions.

Heterogeneous catalysis reactions:

Essential mechanisms of heterogeneous catalysis.

Hydrocarbons synthesis - Fischer-Tropsch.

Synthesis of margarines: hydrogenation reactions.

Zeolites as acid catalysts.

Structure and functions; Isomerization reactions and cracking in refineries. Applications in fine chemical reaction catalysis.

Biocatalysis:

Introduction

Industrial processes involving enzymatic systems.

Head Lecturer(s)

Maria Miguéns Pereira

Bibliography

-         Organometallic Chemistry and Catalysis, 2^nd ed. Didier Astruc, Springer-Verlag Berlin Heidelberg 2007.

-         Industrial Catalysis: A Practical Approach, 2^ª ed., Jens Hagen, John Wiley & Sons, Dordrecht, 2006.

-         Homogeneous Catalysis. Understanding the Art. P. W. N. M., van Leeuen, John Wiley & Sons, Dordrecht, 2004.

-         Organometallics in Synthesis M. Schlosser ed., Jonhn Willey & Sons, Chichester, 1997.

-         Zeólitos. Um Nanomundo ao Serviço da Catálise. M. Guisnet, F. Ramôa Ribeiro, Fundação Calouste Gulbenkian, Lisboa, 2004.

-         "Organic Chemistry", Clayden, Greeves, Warren, Wothers, Oxford University, 2001.

-         “Organometallic Reagents in Synthesis”, P.R. Jenkins, Oxford Sci. Pub., Oxford, 1992.

-         “Transition Metals for Organic Synthesis: Building Blocks and Fine Chemicals”. Ed. M. Beller, C. Bolm, Wiley-VCH, Weinheim, 1998.

-         Fundamentos Y Aplicaciones de la Catálisis Homogénea, L.A. Oro, E. Sola, Zaragoza, 2000.

“Química Síntese e Estrutura. Uma Abordagem Prática” H.D. Burrows, Mariette M. Pereira, Escolar Editora, Lisboa 2006.