Universidad de Jaén

0.- INTRODUCTION

Description of the course. Aim and scope, contents and methodology. Bibliography. Assessment.

COORDINATION CHEMISTRY

1.- COORDINATION CHEMISTRY BONDING (I): VALENCE BOND AND CRISTAL FIELD THEORIES

Historical background. Valence bond theory: uses, advantages and disadvantages. Crystal field theory. Orbital splitting in octahedral, tetrahedral and square-plane ligand fields. Spectrochemical series. Jahn-Teller's effect. Restrictions of the crystal field theory.

Reading homework: Blomstrand & Jorgensen's chains theory.

2.- COORDINATION CHEMISTRY BONDING (II): MOLECULAR ORBITAL THEORY

Experimental covalency evidences of the metal-ligand bond. Molecular orbital theory. Complexes with pi-acceptor and pi-donor ligands.

3.- ELECTRONIC SPECTRA AND MAGNETIC PROPERTIES

Energy levels in the free ions. Racah's parameters. Correlation diagrams: Orgel's and Tanabe-Sugano's plots. Interpretation of the spectra. Magnetic properties. Magneto-structural correlations.

4.- STRUCTURE, STEREOCHEMISTRY AND ISOMERISM

Usual stereochemistries and electronic configuration: Angular overlap model.

Reading homework: Unusual coordination numbers. Non-rigid structrures. Isomerism.

5.- THERMODYNAMIC STABILITY

Stability equilibria and constants. Factors affecting the stability. Chelate, cryptate and macrocyclic effects. Experimental calculation of the stability constants.

Reading homework: Chelate, cryptate and macrocyclic effects.

6.- REACTIONS AND MECHANISMS: SUBSTITUTION AND ELECTRONIC TRANSFER PROCESSES

Substitution reactions in square-plane and octahedral complexes. Associative, dissociative and exchange mechanisms. Trans effect and trans influence. Electron transfer reactions. Outer and inner sphere mechanisms.

Reading homework: Synthetic uses.

7.- INTRODUCTION TO BIOINORGANIC CHEMISTRY

Metals and complexes in biological systems. Oxygen transport and storage. Electron transfer processes. Nitrogen fixation. Pharmacological applications.

Reading homework: Bioinorganic functions.

ORGANOMETALLIC CHEMISTRY 

8.- COMPLEXES WITH PI-ACCEPTOR LIGANDS: METAL CARBONYLS AND NITROSILS

Atomic effective number's rule. Classification of carbonyls. Synthesis and properties. Structure and bond nature. Reactivity. Carbonyl derivatives: carbonylate anions, carbonyl hydrides and halides. Metal nitrosyls: Structure, bond and properties. Complexes with other pi-acceptor ligands.

9.- INTRODUCTION TO ORGANOMETALLIC CHEMISTRY

Introduction. The metal-carbon bond: energy, polarity and reactivity. Factors affecting the stability of the metal-carbon bond. Compounds with sigma and pi metal-carbon bond: Features and kinds of ligands. Pi-olefine compounds. Metallocenes.

10.- ORGANOMETALLIC CHEMISTRY AND CATALYSIS

Homogeneous and heterogeneous catalysis. Organometallics and catalysis.

Reading homework: Examples of homogeneus catalysis.

SOLID STATE CHEMISTRY

11.- STRUCTURE OF SOLIDS

Introduction. Crystalline and amorphous solids. Crystal networks. Close-packing based structures. The hard sphere model (HSM). Structure and bond.

12.- DISORDER AND NON-STOICHIOMETRY

Crystal deffects: points and vacants (Schottky) and interstitial (Frenkel). Linear deffects: Edge and helicoidal dislocations. Non-stoichiometric compounds.

13.- SILICATES

Silica: crystal structure and plymorphs. Silicates: Structure. Classification: Single anion, linear, laminar and tridimensional structures.

14.- METALLIC OXIDES

Classification and bond types. Acid-base character. Most common structures. Mixed oxydes: Classification, structure and properties.

15.- ISO AND HETEROPOLYANIONS

Reading homework: Isopolyanions and heteropolyanions structure. General properties.

EXPERIMENTAL METHODS FOR STRUCTURAL DETERMINATION OF INORGANIC COMPOUNDS

16.- EXPERIMETAL METHODS FOR STRUCTURAL DETERMINATION OF INORGANIC COMPOUNDS

Spectral methods. Thermal methods. Diffraction methods.

Lecture (Theory): 38 hours

Seminars: 20 hours

Tutorial: 2 hours

Students with special educational needs should contact the Student Attention Service (Servicio de Atención y Ayudas al Estudiante) in order to receive the appropriate academic support

Exam on the contents of the course (70% theory plus 30% seminars) for every calls.

This is a full evaluation of the reached competences (Q1, Q3, B2, B9, CE6, CE16) from both theoretical and applied points of view.

Warning: In the assessment, errors in basic questions such as formulation, periodic table, electronic configurations, etc., will entail the total annulment of the question.