C7750 Advanced Coordination Chemistry

Faculty of Science
Autumn 2023

The course is not taught in Autumn 2023

Extent and Intensity
2/0/0. 2 credit(s) (plus extra credits for completion). Type of Completion: zk (examination).
Taught in person.
Teacher(s)
doc. Mgr. Marek Nečas, Ph.D. (lecturer)
prof. RNDr. Jiří Pinkas, Ph.D. (lecturer)
Guaranteed by
prof. RNDr. Jiří Pinkas, Ph.D.
Department of Chemistry – Chemistry Section – Faculty of Science
Supplier department: Department of Chemistry – Chemistry Section – Faculty of Science
Prerequisites
C1061 Inorganic Chemistry I && C2062 Inorganic Chemistry II
Succesful completion of Inorganic Chemistry I-II courses.
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
This course utilizes basic knowledge of chemistry of metal complexes gained in lectures on inorganic chemistry and develops advanced topics of bonding in transition metal complexes, their spectroscopic and magnetic propertes, thermodynamic stability and kinetic behavior in chemical reactions.
Learning outcomes
Upon completing this course, students will be able to:
- describe bonding in transition metal complexes by ligand field theory and molecular orbital theory
- explain behavior of metal complexes in UV-vis, NMR, EPR, Moessbauer spectra
- describe magnetic properties of metal complexes
- understand thermodynamic stability and kinetic behavior of complexes in chemical reactions
Syllabus
  • Introduction. Historical Perspective – A. Werner. Transition metals and d-electron configurations, a coordination complex, metal-ligand bonding, the coordinate bond and Lewis Acid-Base interactions. Types of ligands and their coordination modes. Isomerism: geometric, structural, constitutional, linkage.
  • Bonding in Metal Complexes. d-orbitals, Ligand Field Theory for octahedral and tetrahedral complexes. Effect of inter-electron repulsion – high and low spin electron configurations, pairing energy. Spin-only magnetic moments. Molecular orbital description, MO Theory of octahedral complex σ bonds. Ligand field splitting in octahedral complexes (sigma- and pi-bonding). Factors determining the ligand field splitting, spectrochemical series of ligands and metals - sigma-donors, pi-donors, pi-acceptors (weak and strong field ligands), pi-backbonding. Jahn-Teller effects.
  • Thermodynamics across the first row transition series– Lattice field stabilization energies, Lattice energies, Hydration energies, Variations in ionic radii. Stability constants. Irving-Williams series. Stability of Metal Complexes - Kinetic and Thermodynamic stability. Stepwise formation constants. Chelate and macrocyclic effects.
  • Geometries of Metal Complexes. Tetrahedral molecular orbital diagram and ligand-field splitting. Square planar geometry, trigonal bipyramidal geometry. Role of ligand field vs ligand size in determining complex geometry. Less common oxidation states, mixed-valence complexes.
  • Electronic Spectroscopy. The Colors of TM Complexes. Term symbols. Electronic spectra for transition-metal complexes. Interelectronic repulsion and the nephelauxetic series. Orbital, Laporte and spin selection rules. The Frank-Condon principle. Charge transfer transitions (ligand to metal, metal to ligand and intervalence).
  • Aqueous Solution Chemistry and Magnetism. Redox potentials and aqueous oxidation states of transition metal ions. Ligand-field spectra of d1 – d9 ions.
  • Magnetochemistry. Spin crossovers. Spin frustration. Molecular magnets. NMR and EPR spectroscopy of transition metal complexes.
  • Transition Metals in Low Oxidation States. Carbonyl complexes and organometallic chemistry. MO diagram for CO, 18 electron rule, pi-backbonding. Vibrational spectroscopy of carbonyl compounds.
  • Complexes of Unusual Ligands. Oxygen complexes (mechanism of oxygen transport in haem proteins, model complexes). NO and N2 complexes (N2 fixation in nitrogenase). Complexes of hydrogen.
  • Reaction mechanisms of Substitution and Redox Reactions. Associative and dissociative mechanisms of substitution reactions. Water exchange and complex formation rates. Lability and inertness. Electron transfer by inner and outer sphere mechanisms. Photochemistry. Reactions on coordinated ligands.
Literature
  • Coordination chemistry reviews : an international journal. Edited by A. B. P. Lever. Amsterdam: Elsevier. info
  • Concepts in transition metal chemistry. Edited by Eleanor Crabb - Elaine Moore - Lesley Smart. Cambridge: Royal Society of Chemistry, 2010, 140 s. ISBN 9781849730624. info
  • Introduction to coordination chemistry. Edited by Geoffrey A. Lawrance. Chichester, West Sussex: Wiley, 2010, xiii, 290. ISBN 9780470519318. info
  • Comprehensive coordination chemistry II : from biology to nanotechnology. Edited by Jon A. McCleverty - Thomas J. Meyer. 1st ed. Amsterdam: Elsevier, 2004, xxxi, 266. ISBN 008044332X. info
  • CONSTABLE, Edwin C. Coordination chemistry of macrocyclic compounds. 1st pub. Oxford: Oxford University Press, 1999, 91 s. ISBN 0198556926. info
  • HOUSECROFT, Catherine E. The heavier d-block metals : aspects of inorganic and coordination chemistry. 1st pub. Oxford: Oxford University Press, 1999, 89 s. ISBN 0-19-850103-X. info
  • DVOŘÁK, Dalimil. Chemie organokovových sloučenin přechodných kovů. 1. vyd. Praha: Vysoká škola chemicko-technologická, 1994, 263 s. ISBN 80-7080-209-X. info
  • BLASSE, G. Complex chemistry. Berlin: Springer-Verlag, 1991, 197 s. ISBN 3540534997. info
Teaching methods
Lectures, literature search, student presentations
Assessment methods
There are 3 graded homeworks during the semester. At the end of the course every student will give a short presentation on a selected topic concerning coordination chemistry. Written final exam worth 100 pts, minimum 50 pts to pass. Weights: final test 75%, homeworks 15%, presentation 10%.
Language of instruction
Czech
Further Comments
The course is taught annually.
The course is taught: every week.
The course is also listed under the following terms Autumn 2022, Spring 2024.
  • Enrolment Statistics (Autumn 2023, recent)
  • Permalink: https://is.muni.cz/course/sci/autumn2023/C7750