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.
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.
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.
Centro de Química Estrutural
Complexo I, Instituto Superior Técnico
Av. Rovisco Pais, 1049-001 Lisboa, Portugal