Required in stage
Optional in stage
First term
Second term
Both terms
Not organised
This year
Next year
Alternating years
External
Prerequisites
Taught by
Language of instruction
Duration
Identical coursesAims
The students are familiar with the most important reactions in current organometallic chemistry. They are able to autonomously propose a feasible mechanism for the most important transition metal catalyzed transformations. They are able to design a synthetic plan using the reactions discussed in the classes.
Previous knowledge
The student is familiar with the principles of reaction mechanisms and reactivity in organic chemistry as well as with the basic principles of complex formation. Typically, this knowledge is taught at KU Leuven in the courses Metalen en katalyse, Organic chemistry and Advanced organic chemistry.
Is included in these courses of study
Activities
6 ects. Organometallic Chemistry: Lectures (B-KUL-G0S43a)
Content
Introduction
Rules of Semmelhack and Davies
Hapto-number
Ligand metal binding
Electronic effects in complexes
Steric effects in complexes
Backbonding
Reaction types
Polar, apolar: association/dissociation of the ligand, oxidative addition/reductive elimination, insertion/retro-insertion
Cationic complexes
Nucleophilic attack to a cationic complex
Fe-complexes
Cationic Fe-complexes: reactions, regioselectivity, synthesis, reactions with epoxides
Neutral hapto2-Fe-complexes
Cationic hapto3-Fe-complexes
Cr-complexes
Theory
Deprotonation
Reactions with nucleophiles: aromatic ring contains/does not contain a leaving group
Pd-complexes
Synthesis of hapto1-, hapto2- and hapto3-Pd-complexes
Cross coupling with Pd: Suzuki-, Stille-, Kumada-, Negishi-coupling, Heck-reaction, cascade reactions, …
Olefin metathesis:
Grubbs’, Hoveyda’s, ... catalyst
RCM, ROM, ROMP
C-H activation
Organolithium and organomagnesium compounds
Synthesis and reactivity
Halogen-metal exchange
Directed ortho metallation
Organoboron reagents as cross coupling partners: synthesis and reactivity
Boranes
Boronic acids
Boronic esters
Iridium C-H Borylation
Pd catalysed preparation
MIDA boronates
Potassium trifluoroborate salts
Organosilicon (germanium, tin) synthesis and reactivity
Organozinc reagents
Organozirconium reagents
Organotitanium reagents
Synthesis an reactivity, Ziegler-Natta
Selected topics in cross coupling chemistry (each year a selection of these topics will be taught)
Gold, silver, copper catalysis (coinage metals)
Fluorosulfates (as leaving groups in cross coupling)
Reactions under CO atmosphere, DABSO as SO2 surrogate
Diaryliodonium salts in organometallic synthesis
Nickel catalysis
Rh Carbene chemistry and nitrene chemistry
Isomerisation of alkenes: Rh-, Fe-Catalysts
Course material
Slides and lecture notes, selected papers