C5880 Principles of Stereochemistry

Faculty of Science
Autumn 2011
Extent and Intensity
2/0/0. 2 credit(s) (fasci plus compl plus > 4). Recommended Type of Completion: zk (examination). Other types of completion: k (colloquium).
Teacher(s)
RNDr. Miloš Černík, CSc. (lecturer)
doc. RNDr. Jiří Toužín, CSc. (lecturer)
Guaranteed by
doc. RNDr. Jiří Toužín, CSc.
Department of Chemistry – Chemistry Section – Faculty of Science
Timetable
Thu 9:00–10:50 C12/311
Prerequisites
Successful completion of basic courses of inorganic, organic and physical chemistry, basic knowledge of vector and matrix algebra
Course Enrolment Limitations
The course is also offered to the students of the fields other than those the course is directly associated with.
fields of study / plans the course is directly associated with
Course objectives
The lecture covers the description of chemical bonding and principles of stereochemistry of inorganic, coordination and organometallic compounds. Symmetry properties of molecules, chain and sheet polymers and crystals are described on the basis of symmetry point and space groups. Conformation of both cyclic and acyclic molecules, isomerism of main group and coordination compounds, chirality and stereochemically nonrigid and fluxional molecules are also treated. At the end of this course students should become conversant with basic concepts and models in stereochemistry and should be able
* to determine symmetry of simple molecules and coordination polymers
* to predict molecular geometry using valence shell electron pair and ligand close packing models
* to recognize and sketch all possible isomers for an encountered molecule.
Syllabus
  • Symmetry properties of the molecules: geometric transformations, symmetry elements and operations, equivalent symmetry elements and equivalent atoms, matrix notation for geometric transformations, transformation matrices and their characters. Theorems of group theory: the definition of group, group order, sub- and supergroups, similarity transformation, conjugate elements, classes, isomorphous groups. The symmetry point groups: symmetry operations as elements of symmetry point groups, products of symmetry operations, systematic symmetry classification of molecules. Matrix representation of point groups: reducible and irreducible representations, character tables and their use, reduction of reducible representations, direct product of irreducible representations, correlation tables. Symmetry of chain and sheet polymers: screw axis and glide planes, one-dimensional lattice, translation groups, chain symmetry and line groups, factor groups, symmetry of two-dimensional species, plane grous. Crystal symmetry: three-dimensional lattices and crystal systems, the primitive cell, 14 Bravais lattices, 32 crystal classes, three--dimensional space groups and their subgroups, site symmetry and equivalent positions, orientationally disordered structures, hypersymmetry. Electronic structure of free atoms and ions: quantum numbers of many-electron atoms, symmetry properties of atomic orbitals, parameters of covalent chemical bond, ionic character of covalent bond. Valence--bond (VB) theory: valence states, hybridisation, hybridisation schemes for sigma-orbitals, hybridisation schemes for pí-orbitals, hybrid orbitals as linear combinations of atomic orbitals. Ligand field (LF) theory: splitting of levels and terms in chemical environment (Oh, Td, D4h), construction of energy level diagrams, Jahn-Teller theorem, spectral properties and magnetic properties of complexes, the ionic radii of transition metals, thermodynamic and kinetic consequences of d-orbitals splitting. Molecular orbital (MO) theory: secular equation, the Hűckel approximation, homocyclic pí-systems, open-chain pí-systems, three-centre bonding, metalocenes, applicability of VB, LF and MO theories. Chemical isomerism: definition and chemical significance of isomerism, classification of isomerism, structural isomerism and stereoisomerism, isomerism in coordination compounds, isomerisation reactions, stereospecific substitution, trans-effect. Optical isomerism: asymmetry and dissymmetry, chirality, enantiomorphism and optical activity, racemization reactions, molecules with more than one asymmetric center, diastereoisomers, absolute configuration, optical rotatory dispersion and circular dichroism. Conformational isomerism: rotational isomerism of acyclic compounds, gauche-effect, atropoisomerism, conformational isomerism of cyclic compounds. Shapes and geometries of molecules: the VSEPR model and the shapes of main group molecules, ligand site preferences, pí-bonding and geometry, geometrical consequences of non-bonded interactions, stereochemically nonrigid and fluxional molecules, structure differences in free and crystalline molecules. Stereochemistry of complex compounds: geometries of coordination compounds, structure of inorganic polymers, polyhedral molecular geometries, boron hydride cages, metal cluster compounds.
Literature
  • MORRIS, David G. Stereochemistry [Morris, 2001]. Cambridge: The Royal Society of Chemistry, 2001, vii, 170 s. ISBN 0-85404-602-X. info
  • GILLESPIE, Ronald J. and Paul L. A. POPELIER. Chemical bonding and molecular geometry : From Lewis to Electron Densities. Edited by Petr C. Ford. Oxford: Oxford University Press, 2001, 267 s. ISBN 0-19-510496-X. info
  • ZELEWSKY, Alexander von. Stereochemistry of coordination compounds. Chichester: John Wiley & Sons, 1995, x, 254 s. ISBN 0-471-95057-2. info
  • TOUŽÍN, Jiří and Miloš ČERNÍK. Základy stereochemie anorganických sloučenin. 1. vyd. Praha: Státní pedagogické nakladatelství, 1985, 246 s. info
  • FIŠER, Jiří. Úvod do molekulové symetrie : aplikace teorie grup v chemii. 1. vyd. Praha: Státní nakladatelství technické literatury, 1980, 287 s. URL info
  • Úvod do stereochemie anorganických sloučenin. Edited by Lubor Jenšovský. 1. vyd. Praha: Státní nakladatelství technické literatury, 1979, 165 s. URL info
Teaching methods
Lecture
Assessment methods
oral exam
Language of instruction
Czech
Further Comments
The course is taught annually.
The course is also listed under the following terms Autumn 2007 - for the purpose of the accreditation, Autumn 2010 - only for the accreditation, Autumn 2001, Autumn 2002, Autumn 2003, Autumn 2004, Autumn 2005, Autumn 2006, Autumn 2007, Autumn 2008, Autumn 2009, Autumn 2010, Autumn 2011 - acreditation, Autumn 2013, Spring 2017.
  • Enrolment Statistics (Autumn 2011, recent)
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