Identifying Data

2020/21

Subject (*)

Synthetic Applications of Organometallic compounds

Code

610509112

Study programme

Mestrado Universitario en Investigación Química e Química Industrial (Plan 2020)

Descriptors

Cycle

Period

Year

Type

Credits

Official Master's Degree

2nd four-month period

First

Optional

Language

Spanish

Teaching method

Face-to-face

Prerequisites

Department

Química

Coordinador

Sarandeses Da Costa, Luis Alberto

E-mail

luis.sarandeses@udc.es

Lecturers

Perez Sestelo, Jose

Sarandeses Da Costa, Luis Alberto

E-mail

jose.perez.sestelo@udc.es

luis.sarandeses@udc.es

Web

http://www.usc.es/gl/centros/quimica/curso/master.html

General description

Esta materia é básica na especialidade Química Sintética porque estuda a reactividade dos compostos organometálicos e as súas aplicacións en síntese e catálise. Así mesmo, os conceptos abordados nesta materia son de utilidade noutras de módulos veciños como Estrutura e Reactividade Química, Nanoquímica e Novos Materiais e Química Biolóxica.
Esta materia está integrada na especialidade Química Sintética. Relaciónase coas materias Compostos Organometálicos e Química de Coordinación Avanzada, que recollen aspectos xerais da estrutura e reactividade dos compostos organometálicos e dos complexos metálicos de coordinación.
A utilización dos compostos organometálicos e a catálise por metais de transición son ferramentas fundamentais da química sintética actual, tanto no seu aspecto académico como no industrial. A síntese orgánica actual exponse o desenvolvemento de procesos máis selectivos e sustentables, obxectivos para os que se requiren con frecuencia os compostos organometálicos e a catálise.

Contingency plan

1. Modificacións nos contidos
– Non se realizarán cambios.

2. Metodoloxías
*Metodoloxías docentes que se manteñen
– Sesión maxistral.
– Seminario.
– Proba mixta.

*Metodoloxías docentes que se modifican
– Todas as metodoloxías docentes se levan a cabo mediante Teams.

3. Mecanismos de atención personalizada ao alumnado
– Correo electrónico: permanente.
– Moodle: Diariamente. Segundo a necesidade do alumando.
– Teams: Sesións maxistrais, seminarios, titorías (2-6 h/semán).

4. Modificacións na avaliación
– Seminario: 60%
A avaliación continua terá un peso do 60% na cualificación da materia e constará os seguintes
compoñentes: resolución de problemas e casos prácticos, cuestións durante o curso e asistencia e participación. Pasa de 40% a 60%.

– Proba mixta 40%
Proba mixta que versará sobre os contidos explicados. Común ao resto das universidades participantes no mestrado. Pasa de 60% a 40%.

*Observacións de avaliación:
A proba mixta consistirá nun conxunto de preguntas través de Moodle ou Forms para responder nun tempo determinado.
Non hai restricións de mínimos nos apartados avaliados.
Se o alumnado tivera dificultades para a realización da proba mixta faríase uso de chamadas telefónicas ou se empregaría un método de avaliación asíncrono.
Alumnado con recoñecemento de dedicación a tempo parcial e dispensa académica de exención de asistencia: elaboración de traballos tutelados (60%) e proba mixta (40%).

5. Modificacións da bibliografía ou webgrafía
Non hai modificacións da bibliografía.

Study programme competencies

Code	Study programme competences
A1	Define concepts, principles, theories and specialized facts of different areas of chemistry.
A2	Suggest alternatives for solving complex chemical problems related to the different areas of chemistry.
A3	Innovate in the methods of synthesis and chemical analysis related to the different areas of chemistry
A6	Design processes involving the treatment or disposal of hazardous chemicals
A8	Analyze and use the data obtained independently in complex laboratory experiments and relating them with the chemical, physical or biological appropriate techniques, including the use of primary literature sources
B1	Possess knowledge and understanding to provide a basis or opportunity for originality in developing and / or applying ideas, often within a research context
B2	Students should apply their knowledge and ability to solve problems in new or unfamiliar environments within broader (or multidisciplinary) contexts related to their field of study.
B4	Students should be able to communicate their conclusions, and the knowledge and the reasons that support them to specialists and non-specialists in a clear and unambiguous manner
B5	Students must possess learning skills to allow them to continue studying in a way that will have to be largely self-directed or autonomous.
B7	Identify information from scientific literature by using appropriate channels and integrate such information to raise and contextualize a research topic
B10	Use of scientific terminology in English to explain the experimental results in the context of the chemical profession
B11	Apply correctly the new technologies to gather and organize the information to solve problems in the professional activity.

Learning aims

Learning outcomes	Study programme competences
To understand the basis of catalytic cycles from the point of view of reaction coordinates and potential energy surfaces.	AC1 AC6 AC8	BC5
To understand the applications in synthesis of the diversity of processes of formation of bonds mediated by organometallic compounds.	AC2 AC3 AC6	BC1 BC2 BC4 BC7 BC10 BC11
Propose synthetic sequences with key disconnections based on synthetic processes of organometallic compounds.	AC2 AC3 AC6	BC1 BC2 BC4 BC7 BC11

Contents

Topic	Sub-topic
Topic 1. Energy principles and fundamentals of organometallic catalytic cycles.	• General concepts • Thermodynamics and kinetics of the catalytic cycle of reactions catalysed by transition metals. • Application: Pd catalyzed cross coupling; Synergy between computational and experimental results.
Topic 2. Cross-coupling reactions and Heck reaction.	• Cross-coupling reactions. Generalities. Leaving groups. Metals. Selectivity. • Carbon-carbon bond formation reactions: organometallic compounds of Li, Zn, Al, Zr, Sn, Cu; Compounds of B and Si; Other metals; Enolates. • Carbon-heteroatom bond formation reactions. • Heck reaction. Components of the reaction. Inter- and intramolecular reactions. Asymmetric Heck Reactions. Heck reactions with organometallic species.
Topic 3. Insertion reactions.	• Carbonylative reactions. Generalities. Mechanism. • Carbonylative coupling reactions. • Hydroformylation reactions. • Carbonylation reactions with carbonyl complexes. • Carboxylation. • Decarbonylative reactions and decarbonylative couplings. • Other insertion reactions with zirconium and titanium.
Topic 4. Reactions of n3-allyl complexes.	• Palladium n3-allyl complexes (1. Synthesis and properties; 2. Regioselectivity and stereoselectivity). • Allylic substitution reactions catalyzed by palladium complexes (1. Allylic alkylation; 2. Amination, etherification and allyl reduction; 3. Cyclization reactions through alkene insertion processes; 4. Cycloaddition reactions via trimethylenemethane intermediates) . • Allylic substitution reactions catalyzed by complexes of other transition metals (Iridium, Nickel, Iron, Molybdenum). • Alkylation reactions with alkynes and alenes catalyzed by Rh complexes.
Topic 5. Reactions of electrophilic complexes of alkenes, alkynes, dienes and arenes.	• Alkyl insertion reactions and Heck, Suzuki, etc., tandem reactions. • Insertion reactions mediated by other metals (Zr and Ti). • Electrophilic additions on alkenes and alkynes. • Reaction of Nicholas and Pauson-Khand. • Reactions of alkenes with palladium in high oxidation state. • Synthetic applications of n4-dienyl complexes and n6-arenes.
Topic 6. Reactivity of metal carbenes.	• Characteristics of carbenes. • Carbenes of transition metals. Structure and types. • Transformations involving carbenes of transition metals. • Olefin metathesis.
Topic 7. Activation reactions of C-H bonds.	• Introduction to the activation of C-H bonds: relevancy, difficulties and mechanisms of activation. • Reactions of insertion of carbenes and nitrenes • Ir-catalyzed borilation reactions • Functionalization of alkanes and arenes catalyzed by Pd(II): oxygenation, arylation, halogenation, oxidative Heck reaction.

Planning

Methodologies / tests	Competencies	Ordinary class hours	Student’s personal work hours	Total hours
Seminar	A1 A2 A3 A6 A8 B1 B2 B4 B5 B7 B10 B11	7	18	25
Mixed objective/subjective test	A1 A2 A3 B2 B5	3	0	3
Guest lecture / keynote speech	A1 A8 B1 B2 B7 B10 B11	12	33	45

Personalized attention		2	0	2

(*)The information in the planning table is for guidance only and does not take into account the heterogeneity of the students.

Methodologies

Methodologies	Description
Seminar	Seminars held with teachers of the Master, or with professionals invited from industry, the administration or other universities. Interactive sessions related to the different subjects with debates and exchange of opinions with students. Resolution of practical exercises (problems, test questions, interpretation and processing of information, evaluation of scientific publications, etc.). Additionally, during the seminars the possibility of carrying out other methodologies is contemplated: - Works, individually or in groups, on scientific topics related to the different subjects of the Master. - Oral presentation of papers, reports, etc., including discussion with teachers and students. - Use of specialized computer programs and internet. Online teaching support (Virtual Campus).
Mixed objective/subjective test	A final written exam is scheduled, which will allow to objectively evaluate the degree of assimilation and the ability to apply the contents of the subject by the student. The objective test will include a unique type of questions, which will be related to the structure, reactivity and synthesis of organic compounds, and will allow to determine if the answers are correct.
Guest lecture / keynote speech	Theoretical classes. Lectures (use of blackboard, computer, cannon), complemented with the tools of virtual teaching.

Personalized attention

Methodologies

Seminar

Guest lecture / keynote speech

Description

Two individual or small group tutorials are programmed to check the comprehension of the subject and to complement the student's formation through solving doubts and other questions.

Assessment

Methodologies	Competencies	Description	Qualification
Seminar	A1 A2 A3 A6 A8 B1 B2 B4 B5 B7 B10 B11	Continuous evaluation will have a weight of 40% in the grade of the subject and will consist of the following components: problem solving and practical cases (15%), oral presentation [(practical cases, problems), 10%] and oral questions during Course (10%) and attendance and participation (10%).	40
Mixed objective/subjective test	A1 A2 A3 B2 B5	The final exam will cover all the contents of the subject.	60

Assessment comments
The evaluation of this subject will be done through continuous evaluation and the completion of a final exam. Repeating students will have the same attendance regime for classes as those who study the subject for the first time. Continuous evaluation (N1) will have a 40% weight in the subject's qualification and will consist of the following components: problem solving and practical cases (15%), oral presentation [(practical cases, problems), 10%] and questions Oral during the course (10%) and attendance and participation (10%). The final exam (N2) will cover all the contents of the subject. The qualification of the student will be obtained as a result of applying the following formula: Final note = maximum (0.4 x N1 + 0.6 x N2) N1 being the numeric note corresponding to the continuous evaluation (scale 0-10) and N2 the numerical note of the final exam (scale 0-10).

Sources of information

Basic	Bates, R. (2012). Organic Synthesis Using Transition Metals, 2nd Ed.. Wiley Hegedus, L. S. (1999). Transition Metals in the Synthesis of Complex Organic Molecules, 2nd Ed.. University Science Books

Complementary	Negishi, E., Ed. (2002). Handbook of Organopalladium Chemistry for Organic Synthesis. Wiley De Meijere, A., Bräse, S., Oestreich, M. (2014). Metal-Catalyzed Cross-Coupling Reactions and More. Wiley-VCH Cybulski, A.; Moulijn, J. A.; Stankiewicz, A. (2010). Novel Concepts in Catalysis and Chemical Reactors: Improving the Efficiency for the Future. Wiley-VCH Luther, G. W. (2016). Reactivity of Transition Metal Complexes: Thermodynamics, Kinetics and Catalysis, in Inorganic Chemistry for Geochemistry and Environmental Sciences: Fundamentals and Applications. Wiley Yu, J.-Q. (2016). Science of Synthesis: Catalytic Transformations via C-H Activation Vol. 1 & 2. Thieme Crabtree, R. H. (2005). The Organometallic Chemistry of the Transition Metals, 4th Ed.. Wiley Kazmaier, U. (2012). Transition Metal Catalyzed Enantioselective Allylic Substitution in Organic Synthesis. Springer-Verlag Beller, M., Bolm, C. (2004). Transition Metals for Organic Synthesis, 2nd Ed.. Wiley-VCH Ananikov, V. P. (2015). Understanding Organometallic Reaction Mechanisms and Catalysis: Computational and Experimental Tools. Wiley-VCH

Recommendations

Subjects that it is recommended to have taken before

Industrial Processes and Sustainability/610509104

Organometallic Chemistry/610509111

Advanced Structural Determination/610509103

Structure and Reactivity of Organic Compounds /610509114

Subjects that are recommended to be taken simultaneously

Stereoselective Synthesis/610509113

Subjects that continue the syllabus

Other comments

(*)The teaching guide is the document in which the URV publishes the information about all its courses. It is a public document and cannot be modified. Only in exceptional cases can it be revised by the competent agent or duly revised so that it is in line with current legislation.