Humboldt-Universität zu Berlin - Faculty of Mathematics and Natural Sciences - Department of Chemistry

Homogeneous Catalysis

Oxidative addition – reductive elimination

Oxidative addition of dihydrogen: homolytic bond cleavage of H2 – transition metal hydrides – H2 complexes – Wilkinson´s hydrogenation catalyst – heterolytic bond cleavage of H2.

Oxidative addition of hydrocarbons: homolytic bond cleavage of C–H bonds – Cyclometallation – heterolytic C–H bond cleavage – σ-bond metathesis – C–H bond activation by superacids.

Activation of carbon-halogen bonds: reaction pathways - Collman reagent.


Insertion reactions:

CO insertion into metal-carbon and metal-hydrogen-bonds.

Olefin insertion into metal-carbon and metall-hydrogen-bonds: reaction pathways – transition-metal alkyl complexes – β-H and α-H-eliminations –hydrometallation – hydroformylation – carbometallation – Ziegler Aufbau reaction – Olefin polymerisation (Ziegler-Natta-Catalysts – Phillips-catalyst – Brintzinger-Caminsky catalysts).

Carbene-insertions into metal-carbon and metall-hydrogen-bonds: Seyferth reagent – Synthesis gas chemistry – Monsanto process – Carbonylation of methylacetate - Catalytic hydroformylation – hydrocyanation of olefins - catalytic hydrogenation of olefins – Heck reaction.

Additions of nucleophiles on ligands

Additions on carbonyl and isonitrile ligands: formyl complexes – acyl complexes - Hieber Base reaction - Reppe carbonylation reactions) - additions on carbene-ligands - alkyl exchange reactions - addition on acyl-ligands (carboalkoxylation reactions) - additions on unsaturated hydrocarbons (Davis-Mingos-Green rules) - additions on olefin ligands (Wacker Process).

Additions of electrophiles on ligands: cleavage of metal-carbon bonds by electrophiles – modification of ligands by electrophiles.

Isolobal concept.


C. Elschenbroich, A. Salzer: "Organometallchemie", Teubner Taschenbücher, ISBN 3-519-33501-8, (1993).
J. P. Collman, L. S. Hegedus, J. R. Norton, R. G. Finke: "Principles and Applications of Organotransition Metal Chemistry", ISBN 0-935702-51-2, (1987).
A. F. Holleman - E. Wiberg: "Lehrbuch der Anorganischen Chemie", Walter de Gruyter Verlag, ISBN 3-11-012641-9, (1995).
F. A. Cotton, G. Wilkinson: "Advanced Inorganic Chemistry", Wiley Interscience.