Topic 1. General characteristics of organometallic complexes. |
1) Formalisms: a) oxidation state, b) electronic configuration, coordination number, and 18e- rule, c) classes of ligands. 2) Considerations about the bond. 3) Structural considerations. |
Topic 2. Organometallic reactions mechanisms. |
1) Associative and dissociative mechanism. 2) Oxidative addition and reductive elimination. 3) Insertions and eliminations. 4) Attacks on nucleophilic and electrophilic ligands coordinated to the metal. 5) Transmetalation. |
Topic 4. Carbonylative and decarbonylative reactions. |
1) General Reactivity of metal carbonyls. 2) Carbonylative coupling reactions catalyzed by palladium and carbonylation of alkenes and alkynes. 3) Carbonylations of industrial interest: Monsanto process; hydroformylation (oxo process). 4) Decarbonylative reactions. |
Topic 6. Metal-alkyne complexes. |
1) Structural Aspects. 2) Metal-alkyne stable complexes: complexes of Co as protecting groups of alkynes and Nicholas reaction. 3) Pauson-Khand reaction. 4) alkyne cycloaddition reactions. |
Topic 7. Metal-alkene complexes, metal-diene and dienyl complexes. Reactions via n3-allyl complexes. Metal-arene complexes. |
1) Metal-alkene complexes of palladium and iron. 2) metal-diene: stabilization of allyl cations and nucleophilic addition. 3) Complexos n5-dienyl: synthetic applications. 6) Reactions of allylic substrates catalyzed by Pd, Ni and other metals. 7) Metal-arene complexes of groups 6 and 8 (Cr, Fe, Ru). |