सीएचएम616ए - ऑर्गेनोमेटेलिक यौगिकों का रसायन
Prerequisites: CHM442 or CHM 342
3-0-0-9
Course Contents
Newer aspects of organometallics derived from different elements such as Pd, Cu, Ti, Rh, Ru, Mo, Ni, Fe, Sn, Si, B, Mg, Ce, etc, including chemo-, regio-, stereoselective reactions, asymmetric induction etc, and their application in organic synthesis will be discussed.
Introduction
History of organometallic chemistry; Werner complexes; Coordination number and geometry; Crystal field theory and ligand field theory; Bonding and molecular orbitals.
Ligands
Bonding Types, Charges, and Donor Electrons; Ligand: chelate effect and heptaciy; 18-electron rule: Usefulness and limitation
Lewis Base Ligands: Halide donors, Oxygen ligands, Sulphur ligands, Nitrogen ligands: R3N, R2N-, RN2-; Tris(pyrazolyl)borate, A Few Biologically Important N-Ligands: imidazole, purine, porphyrine
Carbonyls
Phosphines
-bound carbon ligands: hydrides, alkyls, aryls
-bonded carbon ligands: alkene, alkyne, allyl, diene, arenes, arenes, metalacyles
Metallocene and sandwich complexes
-bonded carbon ligands: carbenes, carbines
Bimetallic complexes and Metal Clusters
Metal-metal bond in bimetallic complexes; Clusters; Isolobal analogy; Metal nanoparticles
Elementary organometallic reactions
Ligand substitutions; Oxidative addition; Reductive elimination; Intramolecular insertions/eliminations; Nucleophillic/Electrophillic attacks on coordinated ligands.
Homogeneous catalysis and Catalysts
Introduction; Alkene isomerization; Hydrogenation; Hydroformylation; Monsanto acetic acid process; Alkene polymerization; Cross coupling reactions; Metathesis; C-H activation and functionalization; Oxidation of olefins; Metal Clusters and catalysis
Physical methods in Organometallic chemistry
1H NMR spectroscopy; 13C NMR spectroscopy; 31P NMR spectroscopy; Dynamic NMR, Mass spectroscopy, Isotope effect.
Bio-inspired Organometallic chemistry
Introduction, Coenzyme B12, Nitrogen fixation; Nickel enzyme; Oxygenases
Topics
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Books and References
J. Tsuji, “Transition metal reagents and catalyst innovations in organic synthesis” John-Wiley- & Sons, Ltd, New York, 2000
M. B. Smith “Organic Synthesis” Wavefunction, Inc 2000
H-J. Schmalz, T. Wirth “Organic Synthesis Highlights”, 2003
K. C. Nicolaou, “Classics in Total Synthesis” Vols I-III, Wiley-VCH, 1996; 2003; 2011
"The Organometallic Chemistry of the Transition Metals" by Robert Crabtree (3rd Edition, Wiley).
“The Principles and Applications of Transition Metal Chemistry”, by Collman, Hegedus, Norton and Finke (2nd eds, University Science Books).
“Organometallics” by , Christoph Elschenbroich. (3rd Edition, Wiley)