ECTS credits ECTS credits: 3
ECTS Hours Rules/Memories Student's work ECTS: 51 Hours of tutorials: 3 Expository Class: 9 Interactive Classroom: 12 Total: 75
Use languages Spanish, Galician, English
Type: Ordinary subject Master’s Degree RD 1393/2007 - 822/2021
Departments: Organic Chemistry
Areas: Organic Chemistry
Center Faculty of Chemistry
Call: Annual
Teaching: With teaching
Enrolment: Enrollable | 1st year (Yes)
1. The student must know and understand:
a) the basic processes of organometallic chemistry.
b) the most important synthetic methodologies based in those processes.
2. The student has to be able to design reasonable synthetic routes applying this knowledge.
THEME 1. INTRODUCTION.
General characteristics of the organometallic complexes: types de ligands, number de electrons, oxidation state, dn configuration, etc. Types of metal-ligand bonds. Structural aspects.
THEME 2. MECHANISMS OF THE ORGANOMETALLIC REACTIONS.
Associative and dissociative mechanisms. Oxidative addition and reductive elimination. Insertions and eliminations. Nucleophilic and electrophilic attack to coordinate ligands. Trasmetalation.
THEME 3. CROSS-COUPLING REACTIONS.
Cross-coupling reactions to C-sp3 species.Cross-coupling reactions to sp2 species. Cross-coupling reactions to sp-species.
THEME 4. HECK REACTION.
THEME 5. REACTIONS THROUGH n3-ALLYL COMPLEXES.
Telomerization of 1,3-dienes. Reactions of allylic substrates catalyzed by Pd. Allylic complexes of other metals: Ni, Fe, Co, Mo, W.
THEME 6. REACTIONS OF CARBONYLATION AND DECARBONYLATION.
General reactivity of metal carbonyls. Carbonylative cross-coupling reactions catalyzed by palladium. Carbonylation of alkenes and alkynes. Carbonylations of industrial interest: Monsanto process; hydroformylation (oxo process). Carbonylation reactions with carbonyls of Fe and Co. Decarbonylation reactions.
THEME 7. METAL-CARBENE COMPLEXES.
Fischer carbenes: preparation and reactivity. Dotz reaction. Nucleophilic carbenes (Schrock carbenes). Tebbe reactive. Alkene metathesis. General mechanism. ROMP. RCM. Design of new catalysts.
THEME 8. METAL-ALKYNE COMPLEXES.
Structural aspects. Metal-alkyne stable complexes: complexes of Co as protecting groups of alkynes. Charge stabilization in propargylic position: Nicholas reaction. Pauson-Khand reaction. Catalytic and enantioselective variants. Transition-metal catalyzed cyclooligomerization of alkynes. Other metal-catalyzed cycloaddition reactions of alkynes.
THEME 9. DIENE AND DIENYL METAL COMPLEXES.
Stable complexes of Fe and Mb: preparation and structural aspects; quirality. Dienes protection through complexation. Stabilization of allylic cations. Nucleophilic addition. Complexes h5-dienyl: synthetic applications.
THEME 10. METAL-ARENE COMPLEXES.
Stable complexes with metals of groups 6 and 8. Reactivity. Synthetic applications.
BASIC BIBLIOGRAPHY:
• Hegedus, L. S. "Transition Metals in the Synthesis of Complex Organic Molecules"; University Science Books, Mill Valley, 1999.
• Bates, R. "Organic Synthesis using Transition Metals"; Sheffield Academic Press, Posgraduate Chemistry Series, Blackwell, 2000.
COMPLEMENTARY BIBLIOGRAPHY:
• Beller, M.; Bolm, C. (Eds.) "Transition Metals for Organic Synthesis: Building Blocks and Fine Chemicals", 2nd Ed.; Wiley-VCH, 2004.
• Crabtree, R.H.; Peris Fajarnes, E. "Química organometálica de los metales de transición". Ed. Publicacions de la Universitat Jaume I. 1997
• de Meijere, A.; Diederich, F. (Eds.) "Metal-catalyzed Cross-coupling Reactions", 2nd Ed.; Wiley-VCH, 2004.
Primary bibliographic sources will be also used during the course, with many examples extracted from recent scientific articles being discussed.
After studying this matter, the student should be able of:
- knowing the most important reactions catalyzed or promoted by transition metals and applying them in the design of synthetic routes to complex organic molecules.
- Drawing up coherent mechanistic proposals for metal-catalyzed transformations.
- Recognizing the factors that can have an effect on the progress of an organometallic reaction.
During the development of the course, the student will also be able to acquire a set of general competences such as:
- Aptitude for carrying out bibliographic search (on line data bases, primary bibliography, etc).
- Use of bibliography in english.
- Critical analysis of scientific texts.
- Make an speech about a scientific theme using audio-visual tools (PowerPoint).
- Magisterial classes where the professor will teach the theoretical contents using audio-visual tools (PowerPoint).
- Seminar classes where the student, either individually or in small groups will solve questions and exercises proposed by the professor.
- Dissertation classes where the student will present a critical analysis of a recent paper using audio-visual tools. After the speech, the students will participate in an open discussion about the most important aspects of the paper.
The subject has a page in the Virtual USC.
It will be evaluated:
1. The active participation of the student (50% of the final mark) in the following terms:
- solving previously proposed exercises and question in the seminars.
- preparation of a scientific paper: carry out an critical analysis of a recently published paper from a high impact scientific journal. This critic analysis will be presented both in writing and as a public oral dissertation.
2. The exam of the subject.
In case of exercises or test realized by dishonest means, the "Evaluation rules of students’ academic performance and qualifications" will be of application.
The time of classes and personal work that every student should devote to pass the matter appears summarized in the following table:
__________________________________________________________________________________
ACTIVITY-----ATTENDING HOURS--FACTOR*--HOURS OF PERSONAL WORK--TOTAL HOURS
__________________________________________________________________________________
Theory----------------18------------------1,25-----------------22-------------------40
Seminars---------------4-------------------2--------------------8--------------------12
Speech-----------------5-------------------3--------------------15-------------------20
Text------------------- 3----------------------------------------------------------------3
__________________________________________________________________________________
OVERALL--------------30----------------------------------------45--------------------75
__________________________________________________________________________________
* Factor: it means the number of hours of personal work per each attending hour.
- It requires a good background in organic chemistry.
- The student must revise the basic aspects of the chemistry of the transition metals.
- Regular attending to classes of theory and seminars will be imperative for passing the matter.
Maria Dolores Perez Meiras
- Department
- Organic Chemistry
- Area
- Organic Chemistry
- Phone
- 881814214
- dolores.perez [at] usc.es
- Category
- Professor: University Professor
Carlos Eugenio Saa Rodriguez
Coordinador/a- Department
- Organic Chemistry
- Area
- Organic Chemistry
- Phone
- 881814400
- carlos.saa [at] usc.es
- Category
- Professor: University Professor
| Wednesday | |||
|---|---|---|---|
| 16:00-17:30 | Grupo /CLE_01 | Spanish | Organic Chemistry Classroom (1st floor) |
| Friday | |||
| 16:00-17:30 | Grupo /CLE_01 | Spanish | Organic Chemistry Classroom (1st floor) |
| 06.26.2025 16:00-20:00 | Grupo /CLE_01 | Organic Chemistry Classroom (1st floor) |