Inorganic Reaction Mechanisms   (1133H)

Academic year:

2012/2013.

Attendance requirements:

1103H

ECTS:

8

Study level:

Study program:

Teacher:

Sofija P. Sovilj, Ph.D.

Assistant:

Jelena M. Poljarević, Ph.D.
assistant professor, Faculty of Chemistry, Studentski trg 12-16, Beograd

Hours of instruction:

Weekly: four hours of lectures + four hours of labwork (4+0+4)

Goals:

• Modern concept of inorganic reaction mechanisms enables for students to understand better and broade their knowledge.
• Basic kinetic and thermodynamic principles commonly used in theoretical calculations are discussed to be a thorough coverage of this area.
• Students should have a cosiderable background of chemistry.

Outcome:

• Theoretical and applied knowledge of structure, chemical bonds as well as free energy may be used as a part of further information and to gain a feeling for the excitement in the field.
• A major goal of this course is to provide students that they can read and analyze current research paper and to enhance their ability to critically evaluate such material.

Teaching methods:

Theoretical is held interactive. Practices are based on investigating/teaching principles with full kinetic approaches, mechanisms simulation. Students are teached how to search through scientific literature as well as to present their own results.

Extracurricular activities:

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Coursebooks:

Main coursebooks:

• Dr. Ivan J. Gal: Mehanizmi neorganskih reakcija, Naučna knjiga, Beograd, 1979.
• Lecture abstracts.

Supplementary coursebooks:

• Jim D. Atwood: Inorganic and Organometallic Reaction Mechanisms, Wiley-VCH, NY, 1997.
• Robert B. Jordan: Reaction Mechanisms of Inorganic and Organometallic Systems, Oxford University Press, 1997.

Additional material:

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Lectures:

0 points (4 hours a week)

Syllabus:

Basic Concepts of Chemical Kinetics:

• Rate laws. Integrated rate expressions.
• Equilibrium assumption. Steady-state approximation. Microscopic reversibility. Activation parameters. Constant thermodynamic parameters. Linear free-energy relationships. Chemical relaxation. Kinetic techniques. Reaction profiles.
• Classification of mechanisms and energetic profiles.

Ligand Substitution Reactions on Square-Planar Complexes:

• Substitution reaction. Effect of the entering nucleophile. Leaving-group effects. Other metal centers.
• Trans-effect. Activation parameters. Stereochemistry of square-planar substitution reactions.

Ligand Substitution Reactions on Octahedral Complexes:

• Leaving-group and chelate effects. Effect of the metal. Anation reactions.
• Acid and base catalysis. Stability and inertness. Stereochemistry of octahedral substitution reactions.

Mechanisms of Organometallic Systems:

• Metal carbonyl and nitrosyl complexes.
• Metal effects on reactivity. Solvent effects. Nature of the intermediate.
• Oxidative-addition. Reductive-elimination.
• Mechanisms of homogeneous catalysis.
• Metal complexes catalytic effects on activated carbon-carbon double bonds.

Stereochemistry of Metal Complexes:

• Coordination number (CN) isomerization (CN 5, 6, 7, 8, 9). Metal-metal bonded systems. Metal carbonyl dimers. Trinuclear and tetranuclear clusters. Pseudorotation.

Redox Reaction:

• Electron transfer. Outer sphere electron transfer.
• Inner sphere mechanisms. Multielectron transfer. Non/complementary reactions. Catalytic redox reactions.

Labwork:

10 points (4 hours a week)

Syllabus:

Calculation of the Kinetic Parameters:

• Calculation of the rate constants and the reaction order.
• Calculation of the activation parameters.

Practice:

• Preparation for all the exercises.
• Kinetics of the protolytic reaction under the appropriate conditions 1.
• Kinetics of the protolytic reaction under the appropriate conditions 2.
• Differential and integral calculus of the obtained results.
• Mechanism of the protolytic reaction.
• Kinetics of the ligand substitution reaction in the metal complex under the appropriate conditions 1.
• Kinetics of the ligand substitution reaction in the metal complex under the appropriate conditions 2.
• Differential and integral calculus of the obtained results.
• Mechanism of the ligand substitution reaction in the metal complex.
• Kinetics of a very fast redox reaction under the appropriate conditions.
• Differential and integral calculus of the obtained results.
• Mechanism of a very fast redox reaction.

Presentation:

• Presentation of the corresponding results in an oral form.

Semester papers:

15 points

Colloquia:

15 points

Oral exam:

60 points