Research projects at Lisbon 

 

 

Catalytic and Electrocatalytic Reactions of Small Molecules

 

This ER position, immediately available, is for up to 9 months. It is expected that it can be extended to much longer periods by a subsequent  national post-doc. fellowship.

 

The project will fit within the continued interest of this Group on the activation, by transition metal centres, of small molecules with industrial, environmental or pharmacological significance (like alkenes, alkynes, alkanes, dioxygen, peroxide, oximes, nitriles, carboxamides, amidines, oxadiazolines, etc.), namely searching for alternatives for industrial processes and new reactions with a possible interest in fine chemistry.

It will be initiated with the synthesis and characterization of inorganic and organometallic complexes with transition metals in middle-to-high oxidation states, with O- and N-donor ligands, and the investigation of their reactions with some of the above substrates, in particular towards their catalytic oxidation, whenever possible in aqueous medium. Examples of reactions types to be investigated include the following ones:  functionalization af alkanes to alcohols, ketones, carboxylic acids, etc. under mild reaction conditions; oxygen-atom-transfer reactions to olefins.

The chemical studies will be followed by electrochemical ones, namely attempting to establish redox potential-structure-reactivity relationships, to activate the complexes to further reactions by electron-transfer and to find electron-transfer mediators active in electrocatalytic processes.

Requirements: Knowledge and experience in inorganic and organometallic chemistry, including handling and synthesis of air-sensitive compounds, in catalysis and in electrochemical methods. Strong interest in continuing the studies by a subsequent post-doc. fellowship.

Selected references

1-A.J.L. Pombeiro (ed.)  and C. Amatore (co-ed.) “Trends in Molecular Electrochemistry”, Marcel Dekker / FontisMedia, New York / Lausanne, 2004.

 2- A. Venâncio, M.F.C. Guedes da Silva, L.M.D.R.S. Martins, J.J.R. Fraústo da Silva and  A.J.L. Pombeiro,  “Allenylidene Iron(II) Complexes  and  Their  Deprotonation, Nucleophilic Addition Reactions and Cathodic Protonation toward Alkynyl  Derivatives, a Chemical and Electrochemical Study”, Organometallics, 2005, 24, 4654-4665.

3- A.M. Kirillov, M.N. Kopylovich, M.V. Kirillova, E. Yu. Karabach, M. Haukka, M.F.C. Guedes da Silva and A.J.L. Pombeiro, “Mild Peroxidative Oxidation of Cyclohexane Catalyzed by Mono-, Di-, Tri-, Tetra- and Polynuclear Copper Triethanolamine Complexes”, Adv. Synth. Cat., 2006, 348, 159-174.

4- A.M. Kirillov, M.N. Kopylovich, M.V. Kirillova, M. Haukka, M.F.C. Guedes da Silva and A.J.L. Pombeiro, “Multinuclear Copper Triethanolamine Complexes as Selective Catalysts for the Peroxidative Oxidation of Alkanes under Mild Conditions”, Angew. Chem., Int. Ed., 2005, 44, 4345-4349.

5- P.M. Reis, J.A.L. Silva, A.F. Palavra, J.J.R. Fraústo da Silva and A.J.L. Pombeiro, “Vanadium-Catalyzed Carboxylation of Linear and Cyclic C5 and C6 Alkanes”, J. Catal., 2005, 235, 333-340.

6-  M.N. Kopylovich, V. Yu. Kukushkin, M. Haukka, K.V. Luzyanin and A.J.L.

Pombeiro, “An Efficient Synthesis of Phthalocyanines Based on an Unprecedented Double-Addition of Oximes to Phthalonitriles”, J. Am. Chem. Soc., 2004, 126, 15040-15041.

7-  Q. Li, M.F.C. Guedes da Silva and A.J.L. Pombeiro, “Diorganotin(IV) Derivatives of  Substituted Benzohydroxamic Acids with High Antitumor Acticvity”, Chem. Eur. J., 2004, 10, 1456-1462.

8- M.F.C. Guedes da Silva, J.A.L. da Silva, J.J.R. Fraústo da Silva, A.J.L. Pombeiro, C. Amatore and J.-N Verpeaux, "Evidence for a Michaelis-Menten Type Mechanism in the Electrocatalytic Oxidation of Mercaptopropionic Acid by an Amavadine Model", J. Am. Chem. Soc., 1996, 118, 7568-7573.

 

Cost of living in Lisbon: Accommodation  from ca. 220 euros/month (single room in a shared flat or family); other living expenses: ca. 300 euros/month.

  Contact:         Prof. Armando Pombeiro

        Centro de Química Estrutural

        Complexo I, Instituto Superior Técnico

        Av. Rovisco Pais, 1049-001 Lisboa, Portugal

        FAX: +351.218464455

        Phone: +351.218419237

        E-mail: pombeiro@ist.utl.pt

        www.ist.utl.pt

        http://dequim.ist.utl.pt/english/

        http://myprofile.cos.com/pombeiro