The determination of the rate law. The rate of a reaction and the rate law. Integrated forms of the rate expression. Monophasic unidirectional reactions. Monophasic reversible reactions. Multiphasic unidirectional reactions. Relaxation kinetics. Exchange kinetics. Inclusion of H+ terms in the rate law. The deduction of mechanism. The rate law and mechanism. Activation parameters, thermodynamic functions and mechanism. Linear free-energy relationships. The relationship between the activation entalphy, entropy, and volume with mechanism. Medium effects on the rate. The experimental determination of the rate of reaction. Flow and relaxation methods. Large perturbation. Competition methods. Accessible rate constants using rapid reaction methods. Spectrophotometry. Non-spectrophotometric methods. Batch methods. The study of transients. The characteristics of substitution reactions. Substitution in octahedral complexes. Accelerated substitution of unidentate ligands. Replacement reactions involving multidentate ligands. Substitution in square-planar complexes. Substitution in tetrahedral complexes. Substitution in five-coordinate complexes. Substitution in organized surfactant systems. Substitution in metalloproteins. Oxidation-reduction reactions. Outer sphere reactions. Inner sphere redox reactions. Bridging ligand in inner-sphere redox reactions. Intramolecular electron transfer. Electron transfer in proteins. The modification of ligand reactivity by complex formation. The metal as a collecting point reactant. Promotion of reaction within the metal-bound ligand. Hydrolysis of coordinated ligands. Electrophilic substitution in metal complexes. Masking effects. Disturbance of reaction stoichiometry. Molecular strain alterations. Function of the ligand. Isomerism and stereochemical change. Conformational and configurational Isomerism. Spin equilibria in octahedral complexes. Linkage, geometrical, and optical isomerism. Octahedral, tetra-penta, hepta and octacoordinated complexes. Inversion and proton exchange at asymmetric nitrogen. Inorganic photochemistry. Kinetic factors affecting quantum yields. Photochemistry of CoIII, RhIII and CrIII. Polypiperidine complexes of RuII. Organometallic photochemistry. Photochemical generation of reaction intermediates. Organometallic substitution reactions. Ligand bonding. Metal carbonyl substitution reactions. Dissociation of other ligands. Ligand effects. Complexes with 17 electrons. Substitution on metal carbonyl complexes containing M-M bonds. Ligand substitution reactions on alkyl complexes. Hydride complexes. Nitrosyl, allyl, and other complexes. Homogeneous catalysis by transition metal complexes. Homogeneous hydrogenation of alkanes. Assymetric hydrogenation. Hydroformylation reaction. Wacker acetaldehyde synthesis. Hydrocyanation of 1,3-butadiene. Olephin methatesis. Polymerization of alkenes. Methanol carbonylation.
- OBVEZNA LITERATURA:
R. G. Wilkins, Kinetics and Mechanism of Reactions of Transition Metal Complexes, VCH, Weinheim, 1991.
M. L. Tobe, J. Burgess, Inorganic Reaction Mechanisms, Longman, Harlow, 1999.
J. D. Atwood, Inorganic and Organic Reaction Mechanisms, Wiley-VCH, Inc., New York 1997.
R. B. Jordan, Reaction Mechanisms of Inorganic and Organometalic Systems, Oxford University Press, Inc., Oxford, 2007.
- DOPUNSKA LITERATURA:
J. H. Espenson, Chemical Kinetics and Reaction Mehanisms, McGraw-Hill Companies, Inc., Custom Publishing, New York, 2002.
S. Ašperger, Kemijska kinetika i anorganski reakcijski mehanizmi, HAZU, Zagreb, 1999. (Postoji prijevod izvornika na engleskom iz 2003.)
F. Basolo, R. G. Pearson, Mechanisms of inorganic reactions. A study of metal complexes in solution, Wiley Eastern Private Ltd., 2nd Ed., 1973.
D. Katakis, G. Gordon, Mechanisms of Inorganic Reactions, Wiley-Interscience, New York, 1987.
J. P. Candlin, K. A. Taylor, D. T. Thompson, Reaction of transition metal complexes, Elsevier Publishing Company, 1968 (Postoji prijevod izvornika na ruskom iz 1970.)
E. C. Constable, Metals and Ligand Reactivity, 2. izd., VCH, Weinheim, 1996.