Learning objectives
Design and preparation of coordination and organometallic compounds by the appropriate choice of the reagents and of the experimental conditions. Use of several spectroscopic and analytical tools (FT-IR, NMR, ESI-MS, microanalysis and molar conductivity) for the determination of the stoichiometry and structure of metal containing complexes. Study and rationalization of the reactvity of metal complexes. Ability to carry out reaction under inert atmosphere (Schlenk techniques). Ability to carry out catalytic reactions promoted by metal complexes and rationalization of the results in terms of activity (TON and TOF values) and selectivity. Ability to fill a laboratory book properly.
Prerequisites
Competences on the fundamental concepts of general and inorganic chemistry, organic chemistry, analytical chemistry and spectroscopy.
Course unit content
<p> Frontal lessons - Brief mention of the nature of the coordination bond (CF and MO models). Monodentate and chelating phosphines as ligands. Steric and electronic effects of phosphines. 31P{1H}-NMR spectroscopy for the characterization of phosphine containing complexes. Kinetic and termodinamic template effect. Limitations and merits of the most common investigation tecniques used to establish the structure of metal complexes (IR, NMR, ESI, FAB, XRD, microanalysis, molar conductivity). Low-oxidation states metal complexes and organometallics. Half-sandwich complexes. Catalytic processes promoted by metal complexes. Hydrogen transfer reaction from alcohols to ketones catalysed by ruthenium-containing complexes. <br />
Laboratory practice <br />
1. Synthesis of a Cu(I) complex: Cu(PPh3)2(NO3). Elucidation of the coordination mode of the nitrate ion by FT-IR spectroscopy; evidences of the lability of the nitrate ion by molar conductivity meaurements in dichloromethane and DMF solutions. <br />
2. Synthesis of a tetrahedral Ni(II) complex: Ni(PPh3)Cl2. Evidences of its different stability in coordinating /EtOH) and not-coordinating (CH2Cl2) solvents. <br />
3. Synthesis of a square-olanar Ni(II) complex: Ni(dppe)Cl2. Characterization of the complex by 31P{1H}-NMR and monitoring of the Cl- Br- exchange by the same technique. <br />
4. Synthesis of a tetrahedral Ni(II) complex with PPh3 and study of its interconversion between the tetrahedra and square planar coordination in the solid state</p>
<p>5. Synthesis and characterization by 1H-NMR spectrosocpy of the half-sandwich Ru(II) complex [Ru(p-cymene)Cl2]2. <br />
6. Asymmetric hydrogen transfer from i-PrOH to acetophenone catalyzed by a chiral half-sandwich Ru(II) complex; monitoring of the enantiomeric excess by chiral GC analysis. <br />
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Full programme
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Bibliography
1. Chimica dei composti dei coordinazione, F. Basolo-R. Johnson, Ed. Zanichelli <br />
2. Metals and Ligand Reactivity, E.C. Constable, Ed. VCH <br />
3. Inorganic Chemistry, J.C. Kotz-K.F. Purcell, Ed. Holt Saunders Int. <br />
4. Scientific bibliography <br />
Teaching methods
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Assessment methods and criteria
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Other information
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