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Teaching GuideTerm Faculty of Science |
| Mestrado Universitario en Investigación Química e Química Industrial (Plan 2017) |
 Subjects |
| Synthetic Applications of Organometallic compounds |
| Contents |
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| Identifying Data | 2019/20 | |||||||||||||
| Subject | Synthetic Applications of Organometallic compounds | Code | 610509112 | |||||||||||
| Study programme |
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| Descriptors | Cycle | Period | Year | Type | Credits | |||||||||
| Official Master's Degree | Yearly |
First | Optional | 3 | ||||||||||
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| 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. |
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