Group Coordinator: Pedro Teixeira Gomes
The group activities are centred in the areas of Organometallic/Coordination Chemistry and Catalysis, involving: i) the synthesis of new polyfunctional chelating ligands and their coordination to metal centres to produce complexes with specific electronic and stereochemical properties, ii) the study of their molecular structures, using solution NMR, X-ray diffraction and DFT, and iii) experimental reactivity studies, stoichiometric or catalytic, and computational mechanistic calculations, all together providing an integrated vision of the chemical behaviour of the systems. The application of the new metal complexes as catalysts for several organic reactions or as functional materials is an important objective of the group. The most significant current lines of research are outlined below.
1) Metal Complexes for Enantioselective Oxidation Catalysis (sulfoxidation and epoxidation):
a) Molybdenum, tungsten and vanadium diamine bis(phenolate) complexes
b) Molybdenum, tungsten, vanadium and titanium N-heterocyclic carbene complexes
a) Hydroamination catalysis towards the synthesis of naturally relevant azarings
b) Yttrium complexes with diamido/diamine cyclams as ancillary ligands: syntheses, reactivity and computational studies
c) Catalytic applications of copper complexes anchored by tetraazamacrocycles (Click Chemistry, syntheses of organic azides, oxidation of alcohols)
d) ROP of cyclic esters: PLA incorporating one cyclam ring for drug deliver
e) New antibiotics derived from cyclams
3) Ring-Opening Polymerisation (ROP) of Cyclic Esters with Supported Early Metal Catalysts
4) Synthesis, Characterization and Optimisation of New Nickel(II) and Palladium(II) Complexes Bearing Iminopyrrolyl Chelating Ligands and their Application as Aluminium-Free Catalysts for the Oligo-/Polymerisation of Olefins.
a) Oligo-/polymerisation reactions performed either in organic or in aqueous emulsion media.
b) Immobilization in mesoporous silica and study of their behaviour towards olefin polymerization.
a) Mono- and polynuclear boron complexes for OLEDs and Sensors
b) Boron complexes with Thermally Activated Delayed Fluorescence (TADF)
6) Controlled Polymerisation of Vinyl Polar Monomers Catalysed by Fe(II/III) and Co(II/III) Complexes.
7) Synthesis and Characterization of α-Diimino Copper Complexes as Catalysts for Alkyne-Azide Cycloaddition and Mediators of Atom Transfer Radical Polymerisation (ATRP)
8) Pentabenzylcyclopentadienyl Complexes of Representative Elements: Syntheses, Structures and Catalytic Applications
9) Cytotoxic and Hydrolytic Studies of Titanium Complexes
10) DFT mechanistic studies
a) Spin forbidden reactions
b) Gold catalysed synthesis of furans c) Metal- and diazo-free synthesis of β-lactams
Ana Margarida Sousa Dias Martins
Luis Filipe Coelho Veiros
Pedro Manuel Machado Teixeira Gomes
Clara Sofia Barreiro Gomes
Sónia Duarte Barroso
Luis Gonçalo Andrade Rodrigues Alves
Cláudia Alexandra Carica Figueira
Filipe Miguel Pena Madeira
Patrícia da Silva Lopes
Tiago Filipe Carpinteiro Cruz
Ana Isabel Gomes Peixoto Palha Rodrigues
Joana Fernandes Hipólito
Collaborators & Other researchers
1 – Sónia Barroso, Pedro Adão, M. Teresa Duarte, João C. Pessoa, Ana M. Martins, Vanadium Diaminebis(phenolate) Complexes: Syntheses, Structures, and Reactivity in Sulfoxidation Catalysis, Inorg. Chem. 2010, 49, 7452–7463.
2 – Luis G. Alves, Frédéric Hild, Rui F. Munhá, Luis F. Veiros, Samuel Dagorne, Ana M. Martins, Synthesis and structural characterization of novel cyclam-based zirconium complexes and their use in the controlled ROP of rac-lactide: access to cyclam-functionalized polylactide materials, Dalton Trans. 2012, 41, 14288-14298.
3 – Rui F. Munhá, Joachim Ballmann, Luis F. Veiros, Brian O. Patrick, Michael D. Fryzuk, Ana M. Martins, Dinuclear Cationic Zirconium Hydrides Stabilized by the N,N-Dibenzylcyclam Ancillary Ligand, Organometallics 2012, 31, 4937-4940.
4 – M. Augusta Antunes, Luis G. Alves, Sónia Namorado, José R. Ascenso, Luis F. Veiros, Ana M. Martins, Hydride Abstraction from [MCpBz(CO)3H] (M = Mo, W; Cp-Bz = C5(CH2Ph)5): New Cationic Complexes Stabilized by η5:η2-C5H4:C6H5 Bonding of the Pentabenzylcyclopentadienyl Ligand, Organometallics 2012, 31, 4387-4396.
5 – Luis F. Veiros, Maria José Calhorda; Indenyl effect in dissociative reactions. Nucleophilic substitution in iron carbonyl complexes: a case study, Dalton Trans. 2011, 40 (42), 11138–11146
6 – Xueliang Huang, Bo Peng, Marco Luparia, Luis F. R. Gomes, Luís F. Veiros, Nuno Maulide; Gold-Catalyzed Synthesis of Furans and Furanones from Sulfur Ylides, Angew. Chem. Int. Ed. 2012, 51 (35), 8886–8890.
7 – Luis F. R. Gomes, Luís F. Veiros, Nuno Maulide, Carlos A. M. Afonso; Diazo- and Transition Metal-Free C-H Insertion: a Direct Synthesis of β-lactams; Chem. Eur. J. accepted.
8 – D. Suresh, Patrícia S. Lopes, Bruno Ferreira, Cláudia A. Figueira, Clara S. B. Gomes, Pedro T. Gomes, Roberto E. Di Paolo, António L. Maçanita, M. Teresa Duarte, Ana Charas, Jorge Morgado, Maria José Calhorda, Tunable Fluorophores based on 2-(Arylimino)pyrrolyl Chelates of Diphenylboron: Synthesis, Structure, Photophysical Characterization and Application in OLEDs, Chem. Eur. J. 2014, 20, 4126-4140.
9 – Lidong Li, Patrícia S. Lopes, Cláudia A. Figueira, Clara S. B. Gomes, M. Teresa Duarte, Vítor Rosa, Christophe Fliedel, Teresa Avilés, Pedro T. Gomes, Cationic and Neutral (Aryl-BIAN)Copper(I) Complexes containing Phosphane and Arsane Ancillary Ligands: Synthesis, Molecular Structure and Catalytic Behaviour in Cycloaddition Reactions of Azides and Alkynes, Eur. J. Inorg. Chem. 2013, 1404-1417.
10 – Lidong Li, Clara S. B. Gomes, Pedro T. Gomes, M. Teresa Duarte, Zhiqiang Fan, New Tetradentate N,N,N,N-chelating α-Diimine Ligands and Their Corresponding Zinc and Nickel Complexes: Synthesis, Characterisation and Testing as Olefin Polymerisation Catalysts, Dalton Trans. 2011, 40, 3365-3380.