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UE Coordination and supramolecular chemistry

Degrees incorporating this pedagocial element :

Description

Goal: These lectures will introduce you into the world of coodination chemistry both on a synthetic and a physico-chemical points of view. 

Content:

I. General concepts in coordination chemistry

  • Metal ions and ligands
  • Nomenclature of complexes
  • Geometry of complexes with different coordinence
  • Isomerism in coordination compounds

 II. Thermodynamic and kinetic approaches of complexes in solution

  • Formation constants: definition and experimental determination
  • Chelate effect, a central concept in coordination and supramolecular chemistry
  • Applications to supramolecular recognition of cations
  • Inertia and lability, essential kinetic notions for understanding complexes reactivity
  • Synthesis of complex dedicated ligands: crown-ethers, Schiff bases, polypyridine, ...

III. Electronic structure of metal complexes

  • Counting electrons in complexes: the Green's method
  • 16/18 electrons rule
  • Reactions implying metal complexes
  • Application to homogeneous catalysis
  • From crystal field to ligand field
  • Construction of Molecular Orbitals diagrams of octahedral metal complexes
  • Insight into spectroscopic series

IV. Optical properties of metal complexes

  • Spectroscopic terms of metal complexes including lanthanide complexes
  • Electronic spectroscopy of metal complexes
  • Emission of light by metal complexes

V. Magnetic properties of monometallic complexes

  • Origins of the magnetic properties of metal complexes
  • Magnetic susceptibility
  • From Van Vleck equation to Curie law
  • Departures from Curie law
  • Spin Cross-Over phenomenon: from definition to applications

Article Analysis

Every student will study and present an article dealing with an application strongly related to the contents of the lecture.

Practical teachings:

 

Four topics of the lectures will be illustrated during four hours experimental work sessions:

  • Synthesis and study of the luminescent properties of lanthanide complexes

  • Biomimetic model of molybdic oxo-tranferase enzyme

  • Synthesis and properties of a iron(II) spin Cross-Over compound [1]

  • Syntheis and study of a mixed-valence compound

To anticipate the Lab work, the practical work is written by each student in a dedicated Labwork notebook [2].

[1] A. Vallée et al., J. Chem. Educ. 2013, 90, doi: 10.1021/ed4000487

[2] A. Eisenberg J. Chem. Educ. 1982, 59, 1045.

Recommended prerequisite

Prerequisites: Basics knowledge of general chemistry (electronic structure of the elements, thermochemistry...), in group theory and in coordination chemistry (general definitions, crystal field theory)

Bibliography