Main Research Areas and Methods
His research activities in the general fields of Coordination, Inorganic, Bioinorganic and Organometallic Chemistries, Catalysis and Electrochemistry have been developed within the following areas whose systematic study has been often introduced by him (his Group) into his research Centre:
- Activation of small molecules with biological, industrial or environmental interest orrelated ones (such as alkanes, carbon dioxide, carbon monoxide, alkynes, phosphaalkynes, isocyanides, dinitrogen, nitriles, cyanamides, nitric oxide, oximes, olefins, azides, cyanates, etc.) by transition metal centres, and developing their application in metal-mediated synthesis and catalysis, namely by searching for mimetic systems of biological processes (e.g. catalysed by peroxidases, particulate methane monooxygenase, nitrile hydratases and nitrogenases), alternatives for industrial processes and new types of molecular activation with significance in fine chemistry.
Within this general area, the following themes can be mentioned, generally aiming the establishment of active systems under mild, environmentally tolerable and sustainable conditions:
Catalytic functionalization of alkanes (for the
single-pot syntheses of added value compounds,e.g., alcohols, ketones,
carboxylic acids, esters or
° Catalytic aerobic oxidation of alcohols to aldehydes and ketones;
° Catalytic C-C coupling (e.g., Suzuki-Miaura, Heck, Sonogoshira types);
° Catalytic C-C coupling of nitroaldol or Henry type;
° Metal-mediated synthesis of organo-nitrogen compounds (e.g., oxadiazolines, oxadiazoles, carboxamides, acetylamides, imidoylamidines, iminoisoindolinones, phthalimides, phthalocyanines, cyano-olefins or tetrazoles);
° Non-covalent interactions in synthesis, including, e.g., Resonance Assisted Hydrogen-bond (RAHB) and Pnicogen bond promoted reactions (e.g., isomerizations, activation to nucleophilic attack, liberation of ligands);
° Polynuclear, supramolecular and polymeric assemblies, synthesized by self-assembly, with interesting magnetic, sorption and/or catalytic properties; crystal engineering of coordination compounds;
° Coordination and organometallic chemistries and catalysis in aqueous media, by using new hydrosoluble catalysts;
° High pressure catalysis and catalysis in supercritical fuid media;
° Bioinorganic and biological chemistries, focusing on biomimetic catalytic systems, synthesis and toxicity evaluation of new metal complexes with anti-tumor activity, and identification of biological targets in the cells;
- Molecular Electrochemistry of coordination and organic compounds, namely towardsapplications in electrosynthesis, electrocatalysis and in mechanistic studies, as well as in the establishment of potential-structure relationships, and in the induction of chemical reactivity by electron-transfer.
- Mechanisms of fast chemical (proton transfer) or electrochemical reactions (in the above fields).
- Theoretical studies applied to the interpretation of the structure and reactivity, and search for the reaction mechanisms of coordination compounds.
For the purpose, various techniques and methods (with the acquisition of the corresponding required instrumentation) have been brought in the research Centre by himself and his Group, namely for:
- catalysis under unconventional conditions, such as, metal-free, solvent-free, microwave assisted, in supercritical fluids or in ionic liquids;
- high pressure gas reactions and catalysis (since 1999, with the cooperation of Prof. A. Palavra);
- conventional molecular electrochemistry (since 1980, e.g. cyclic voltammetry, controlled potential electrolysis and, more recently, electrocatalysis);
- unconventional molecular electrochemistry (since 1990, including the use of ultramicroelectrodes in fast voltammetry, the development and use of digital simulation methods in cyclic voltammetry and their application to mechanistic studies of electrode processes involving fast reactions induced by electron-transfer, in electrocatalysis, etc.);
- stopped-flow spectrophotometry (since 1990, applied to the kinetic investigation of fast reactions, e.g. protonations, in Coordination Chemistry);
- mass spectrometry (including fast atom bombardment, FAB-MS) and its coupling to gas-chromatography (GC-MS) (since 1990, applied to the identification of compounds, e.g. reaction products, and to the induction and monitoring of reactions in FAB conditions);
- thermogravimetry (since 2009);
- microwave promoted synthesis (since 2001);
- catalysis in supercritical fluid (since 2007, with the cooperation of Prof. A. Palavra).
- The application of digital simulation to the analysis of NMR spectra as well as the extension of NMR spectrometry to various then less-common nuclei have also been introduced (since 1991 and 1997, respectively) into his research Centre by his Group.
- Coordination chemistry of small molecules.
- Metal-mediated synthesis of organic compounds.
- Transition metal and organometallic chemistries in aqueous media.
- High pressure gas reactions.
- Reactions in supercritical fluid medium.
- Microwave assisted reactions.
- Non-covalent interactions in synthesis.
- Self-assembly of polynuclear and supramolecular structures.
- Crystal structure design and growth (crystal engineering).
- Complexes with multiple metal-carbon bonds.
- Electrochemistry of complexes.
- Mechanisms of reactions.
- Multinuclear NMR spectrometry.
- Mass spectrometry.
Projects (under his responsibility)
(FCT,Foundation for Science and Technology. ICCTI , Institute for the International Scientific and Tecnological Cooperation.JNICT - National Board for Scientific and Technological Research.CNR - National Research Council (Italy).CNRS - National Centre for Scientific and Technological Research (France). HMC - Human Capital and Mobility programme. POCTI, Operational Programme on Science, Technology and Innovation.PEDIP, Specific Programme for the Development of the Portuguese Industry).
- Catalytic Alkane Functionalization towards Sustainable Organic Synthesis (CAFSOS), (Project PTDC/QEQ-QIN/3967/2014, FCT) (since 2016) (199 kEuro).
- Catalysis and Sustainability (FCT PhD Programme, 24 PhD fellowships) (Programme Director) (since Jan., 2014) (1.209 million Euro).
- Metal-mediated and Metal-catalyzed Conversions of Isocyanides, Russian Science Foundation Project (14-43-00017) for Creation and Development of International Groups (sinceAugust 2014) (Portuguese team leader. Coordinator: V.Yu Kukushkin).
- Coordination Chemistry and Catalysis (former Coordination Chemistry and Molecular Electrochemistry, Synthesis and Catalysis), Group 1 (Centro de Química Estrutural), FCT(since 2015) (founder) (405kEuro, 2015-17).
- Single-Pot Carboxylation of Alkanes under Mild Conditions, (Project PTDC/QUI-QUI/102150/2008, FCT) (2010-13)(143 kEuro).
- GC-MS, [Programme PO 002 (Inovation and Scientific and Technological Research), MO 003 (Development of a Modern Network of R&D Institutions), Project 6811 (Consolidation of Scientific Re-equipment of S&T Institutions), sponsored by FCT, since 2010] (81.4 kEuro).
- Coordination Chemistry and Molecular Electrochemistry, Synthesis and Catalysis, Group V (Centro de Química Estrutural), FCT (2008-14) (founder).
- Catalytic Carboxylation of Alkanes (Project POCI/QUI/58821/2004, sponsored by the POCI 2010 Programme, FCT, 2005-07; project PPCDT/QUI/58821/2004, 2008-09) (73 kEuro).
- Chemical Synthesis and Catalysis (Project CONC-REEQ/543/2001, National Programme for Re-Equipping Science) (2005-09) (Coordinator) (205.5 kEuro).
- Direct Conversion of Methane into Carboxylic Acid (Project supported by a technology transfer agreement with Jiangsu SOPO Corp., since 2005) (80,000 USD).
- Transition Metal Chemistry and Catalysis in Aqueous Media [Project MRTN-CT-2003-503864, Human Resources and Mobility (HRM) Marie Curie Research Training Network (RTN)] (Portuguese team leader). Other participants: Prof. M. Peruzzini (Florence) (Coordinator), Prof. F. Joó (Debrecen, Hungary), Prof. O. Lev (Jerusalem), Prof. A. Lledós (Barcelone), Prof. J.-P. Majoral (Toulouse), Prof. R. Perutz (York), Prof. R. Poli (Dijon), Prof. A. Romerosa (Almería, Spain), Prof. E. Shubina (Moscow) and Prof. R. van Eldik (Erlangen, Germany) (2004-07) (budget for the Portuguese team: 184.9 kEuro).
- Early-Late Multinuclear Metal Systems on Design and Development of New Materials (NATO Collaborative Linkage Grant PST. CLG. 979289). Other participants: Prof. V. Yu. Kukushkin (St. Petersburg State University, Russia) and Prof. P. Sobota (Wroclaw University, Poland) (2003-06) (12 kEuro).
- Metal-based Synthons with Pharmacological Significance (Project POCTI/QUI/43415/2001, sponsored by the POCTI programme, FCT) (2002-05) (98.5 kEuro).
- Coordination Chemistry and Molecular Electrochemistry, Group V (Centro de Química Estrutural), FCT (2000-07) (founder).
- Coordination and Reactivity of Organonitriles, Cyanamides and Derived Species (sponsored jointly by ICCTI and the CNR, Italy). Co-responsibility: Prof. R.A. Michelin (University of Padova) (1999-2001).
- "Oxidation of Saturated Hydrocarbons" (Project PRAXIS/POCTI /2/2.1/QUI/193/94, sponsored by the PRAXIS XXI and the POCTI Programmes) (1998-2002).
- The Chemistry of Platinum Group Metals with N-Donor Ligands: Structure-Reactivity and Structure-Biological Activity Relationships. Co-responsibility: Prof. V.Yu Kukushkin (St. Petersburg State University, Russia) (since 1998).
- "Activation of Phosphaalkynes by Transition-Metal Centres" (sponsored by the CRUP / The British Council, Treaty of Windsor programme). Co-responsibility: Prof. J. Nixon (University of Sussex) (1997-99).
- "Chemical and Electrochemical Investigation of Some Transition Metal-Promoted Reactions of Alkynes, Diazoalkanes, Cyanamide and Derived Species" [sponsored jointly by ICCTI (JNICT) and the CNR, Italy]. Co-responsibility: Prof. R.A. Michelin (University of Padova) (1997-98).
- "Activation of Small Molecules", FCT / JNICT (1996-99).
- "Molecular Electrochemistry of Coordination Compounds", FCT / JNICT (1996-99).
- "Chemistry and Redox Properties of Palladium or Platinum Complexes with Multiple Bonded C,N-Donor Ligands" (sponsored jointly by JNICT and the CNR, Italy). Co-responsibility: Prof. R.A. Michelin (University of Padova) (1995-96).
- "Multiple Metal-Carbon Bond Species in Selective Processes" (Project ERBCHRXCT940501, Human Capital and Mobility EC Network) (participant in charge of the Portuguese team). Other participants: Prof. S. Maiorana (Milan) (Coordinator), Prof. P.H. Dixneuf (Rennes), Prof. K.H. Dötz (Bonn), Dr. J.M. Moreto (Barcelona), Prof. S. Thomas (London) and Prof. J. Gimeno (Oviedo) (1994-97).
- "Development of Mimetic Systems of Fundamental Biological Processes with Environmental and Economical Relevance" (Project PRAXIS/2/2.1/QUI/03/94, sponsored by the PRAXIS XXI Programme for Scientific and Technological Research) (1994-99).
- "Electrochemistry of Transition Metal Complexes? [project sponsored by INIC (1985-1992) or JNICT (1993-95)] .
- "Activation of Unsaturated Small Molecules by Palladium or Platinum Metal Centres, a Chemical and Electrochemical Investigation" (project sponsored jointly by JNICT and the CNR, Italy). Co-responsibility: Dr. R.A. Michelin (University of Padova (1993-94).
- "Activation and Electrochemistry of Unsaturated Small Molecules of Biological or Industrial Significance - Nitric Oxide and Cyanamide" (Project STRDA/CEN/450/92, sponsored by the STRIDE Program, Measure A) (1992-95).
- "Mechanisms of the Activation of Metal-Ligand Bonds by Electrochemistry with Ultramicroelectrodes. Application to the Study of Model Reactions for the Activation of Small Molecules" (project sponsored jointly by INIC, JNICT and CNRS, France). Co-responsibility: Dr. C. Amatore (École Normale Superieure, Paris) (1992-96).
- "Chemistry and Electrochemistry of Low-Valent Palladium and Platinum Complexes with Unsaturated C-N Ligands" (project sponsored jointly by INIC, JNICT and the CNR, Italy). Co-responsibility: Dr. R.A. Michelin (University of Padova) (1991-92).
- "Synthesis and Mechanistic Studies in Bioinorganic Chemistry" [sponsored by the CIENCIA (Science) Program, Sub-program III - Global Support to the Scientific and Technological System, Infrastructures for Research and Development, Measure M] (1990-97) (Coordinator).
- "Molecular Electrochemistry of Coordination Compounds - Application of Ultramicroelectrodes" (Project PMCT/C/CEN/339/90, sponsored by JNICT) (1990-94).
- "Investigation of the Mechanisms of Proton Transfer Reactions, in Coordination Compounds, by Stopped Flow Spectrophotometry" [project sponsored by the ICCTI (JNICT)/The British Council protocol]. Co-responsibility: Dr. R. Henderson (Nitrogen Fixation Laboratory, Norwich (1990-97).
- "Chemistry and Electrochemistry of Coordination Compounds with Multiple Phosphorus-Carbon Bonds" (project sponsored by the CRUP/The British Council, Treaty of Windsor programme). Co-responsibility: Prof. J. Nixon (University of Sussex) (1989-92).
- "Low-Valent Transition Metal Carbene Complexes" (project sponsored jointly by INIC and the CNR, Italy). Co-responsibility: Dr. R.A. Michelin (University of Padova) (1989-90).
- "Chemical/Electrochemical Activation of Compounds with Unsaturated Triple Bonded Carbon" (project 87.47/QUI sponsored by JNICT under the Mobility Programme for S&T) (1988-90).
- "Application of Nitrogen Fixation Metal Sites in Homogeneous Catalysis. Reactions of Alkynes" [joint research programme ("acção integrada") with the Federal Republic of Germany sponsored by the CRUP and by the DAAD]. Co- responsibility: Prof. I. Ugi and Dr. R. Herrmann (University of Munich) (1987-89).
- "Coordination Chemistry of Dinitrogen and Related Molecules" [project sponsored by INIC (1985-1992) or JNICT (1993-95)] .
- "Studies on the Chemical and Electrochemical Properties of Small Molecules Activated by Nitrogen Fixation Metal Sites" (project no. 216.80.56 sponsored by JNICT, 1980-83).
- "The Preparation, Properties and Chemical Reactions of Isocyanide, Carbene and Carbyne Complexes of the Early Transition Metals" (project sponsored by the NATO research grant no. 1604). Co-responsibility: Dr. R.L. Richards (Unit of Nitrogen Fixation, Univ. Sussex) (1978-81).
- "Isocyanide and Nitrogen Fixation" (project sponsored by INIC) (1976-1984).