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Reactions based on the chemistry of transition metals play an important role both in the chemical industry and in the organic synthesis. This course is divided into two parts. In the first part the students familiarize themselves with basic principles of the chemistry of transition metals, with the reactions in coordination sphere and with chemical properties of common ligands. The second part deals with an application of this chemistry in some important industrial processes and especially in the organic synthesis.
Last update: SMIDOVAL (07.01.2010)
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Students will be able to: distinguish basic types of reactions which occur in the coordination sphere of transition metals understand the mechanisms of transition metals catalyzed reactions which are used in organic synthesis propose synthesis of organic compounds using chemistry of transition metals Last update: Dvořák Dalimil (10.04.2014)
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Student has to gain at least 70% from two written tests during the semester and to pass the oral exam. Last update: Dvořák Dalimil (07.05.2014)
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R Skripta: D. Dvořák: Chemie organokovových sloučenin přechodných kovů (VŠCHT 1993). A L.S. Hegedus: Transition Metals in the Synthesis of Complex Organic Molecules (University Science Books, Sausalito, California, 1999). Last update: Dvořák Dalimil (24.04.2014)
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1. Formalism (oxidation state, d-electron configuration, 18-electron rule), bonding in organometallic compounds, classification of ligands, electron book keeping. 2. Ligands bound by s-bond - halides, oxygen and nitrogen ligands, phosphines, hydrides, s-alkyls, s-alkenyls and s-aryls, acyl complexes. Ligand bound by both s- and p-bonds - carbonyls, carbene complexes. 3. Ligand bound by more than one atom - h2-alkene, h4-diene, h6-arene, h3-allyl and h5-dienyl complexes. 4. Reactions in coordination sphere of transition metals - ligand substitution, oxidative addition and reductive elimination. 5. Reactions in coordination sphere of transition metals - insertion and deinsertion, nucleophilic attack on ligands coordinated to transition metals, reactions of coordinated alkenes, arenes and polyenes with nucleophiles. 6. Electrophilic attack on ligands coordinated to transition metals, metalacycles. 7. Homogeneous catalysis - hydrogenation, hydrosilation, hydroboration, hydrocyanation. 8. Homogeneous catalysis - alkene polymerisation and oligomerisation, cyclooligomerisation of 1,3-dienes, polymerisation and cyclooligomerisation of alkynes, hydrocarbonylation. 9. Synthetic applications of transition metal hydrides - reduction, synthetic applications of organocuprates, functionalized organocuprates, applications of complexes obtained by insertion of alkenes and alkynes, hydrozirconation. 10. Synthetic applications of complexes formed by transmetalation + insertion, and complexes formed by oxidative addition + insertion. 11. Cross-coupling reactions, Heck reaction, carbonylations, amination of arylhalides, application of bulky electron-rich phosphines and NHC ligands. 12. Synthetic applications of transition metal carbene complexes, alkene and alkyne metathesis, metal-catalysed decomposition of diazo compounds. Synthetic applications of alkene, alkyne, and dienyl complexes. 13. Synthetic applications of h3-allyl transition metal complexes, asymmetric allylic substitution. 14. Synthetic applications of transition metal h6-arene complexes of chromium and iron, catalytic C-H activation. Last update: Dvořák Dalimil (04.03.2014)
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Dalimil Dvořák: Chemie organokovových sloučenin přechodných kovů: http://uoch.vscht.cz/cz/download/metalika.pdf Last update: Dvořák Dalimil (10.04.2014)
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| Coursework assessment | |
| Form | Significance |
| Oral examination | 100 |