Project Description

"PALLADIUM" is a Network in the field of Homogeneous Catalysis and Organometallic Chemistry (contract N° HPRN- CT- 2002-00196 ) inside the Fifth Framework Programme involving seven laboratories of different European Countries.


The aim of this project is the synthesis of new products through the development of new catalysts, based on palladium compounds. Palladium is an extremely versatile catalyst; it adopts many valences states, colours and geometries to carry out all type of carbon-carbon bond formations, often in high selectivity and enantioselectivity. Four main products and reactions have been selected for this project:

  • Co- and ter-polymerization reaction of carbon monoxide and olefins, yielding linear, perfectly alternating polyketones, a new family of polymers. Control of stereochemistry in more advanced applications is an issue.

  • Similar catalysis to get oligomers, which, after modification, function as resins. Control of molecular weight and composition is an issue.

  • The amidocarbonylation reaction, which makes directly amino acids from small molecules. Enantioselectivity is a key issue.

  • The alkoxy or hydroxycarbonylation of alkenes to form acids and esters. Rates and (enantio)selectivity are the key issues.

A catalysis project consists of several steps schematically reported below:

  • The design and synthesis of new ligands;

  • Synthesis of metal complexes;

  • evaluation of the catalytic activity of the new complexes toward co- and ter-polymerization reactions, oligomerisation and carbonylation reactions;

  • identification and characterization of the products, including molecular weight distribution of polymers;

  • investigation of the catalytic cycle;

  • identification by in situ studies of the catalytic intermediates and resting states;

  • kinetic modelling;

  • molecular modelling.


The Network constitute an excellent basis for training doctorate and post-doctorate (Young Researchers) in an emerging field of research. The different product areas ensure a broad training for the Young Researchers in bulk polymers and chemicals, resins, fine chemicals, pharmaceuticals.

The Young Researchers will visit at least another laboratory than their host by working on different aspects of the same problem. The complementarity of the technical skills, the particular fields of ligand chemistry and catalysis and equipment will dictate the technical part of the training programme. Moreover, they will be trained in the use of specialised techniques. The training offered by the Teams of the Network is schematically reported below:

  • Team UNITS : homogeneous catalysis, high-pressure reactions, X-ray structural characterization by means of synchrotron radiation, chemical systems based on Nitrogen ligands;

  • Team UAMSK : high tech and high pressure NMR, non traditional solvents (sc CO 2), chemical systems based on Nitrogen ligands;

  • Team TU/e : in situ studies of catalysts, kinetics, molecular modelling, chemical systems based on Phosphorus ligands;

  • Team CNR.ICCOM : high pressure NMR, kinetics, high-pressure reactions under constant pressure, chemical systems based on both Nitrogen and Phosphorus ligands, characterization of polymeric materials by NMR, IR and intrinsic viscosity measurements, powder and single-crystal X-ray analysis, theoretical calculations (ab initio, extended Huckel);

  • Team ULP : homogeneous catalysis, synthesis of chiral igands, chemical systems based on hemilabile P-N and P-O ligands;

  • Team URV : synthesis of chiral ligands, homogeneous catalysis, high pressure NMR, in situ studies of catalysts, non traditional solvents (sc CO 2 );

  • Team ETHZ : study of steps responsible of stereochemical control, synthesis of chiral ligands, chemical systems based on N-N, P-P and P-N ligands.

The Young Researchers will participate in all the Meetings organised by the Network (the Annual Workshops and the two 3-day Symposia). In particular, the Annual Workshops will be dedicated to the Young Researchers only, who present their results both as oral communications and posters. The Young Researchers will attend international conferences. Seven industries (INEOS Acrylics, DSM, Shell Chemicals, Aventis, Epsol, YPF, Bayer, Institut Francais du Petrol) are willing to accept Young Researchers of the Network in their laboratories for periods of about three months.



Prof. Giovanni Mestroni
Network Coordinator
Università di Trieste
Dipartimento di Scienze Chimiche
Via Licio Giorgieri 1
34127 Trieste Italy
phone: +39 040 5583956
Fax: +39 040 5583903

Dr. Barbara Milani
Contact Person
Università di Trieste
Dipartimento di Scienze Chimiche
Via Licio Giorgieri 1
34127 Trieste Italy
phone: +39 040 5583955
Fax: +39 040 5583903


Specific action in the Network

  • Synthesis of N-N ligands, in particular phenanthrolines with an alkyl substituent in position 3; - Synthesis and characterization, both in solid state and in solution, of palladium compounds sharing new ligands with other groups; - Copolymerization of CO/styrene and cooligomerization of CO/ethylene and of CO/styrene; - Terpolymerization of CO/ethylene/styrene, CO/styrene/substituted styrene, CO/ethylene/polar olefins and CO/styrene polar olefin. In all the catalytic reactions the catalyst precursors are shred with other Teams inside the Network.


Prof. Dr. Kees Elsevier

Universiteit van Amsterdam
Institute of Molecular Chemistry
Nieuwe Achtergracht 166
1018 WV Amsterdam The Netherlands
phone: +31 20 5255653
Fax: +31 20 5255653


Specific action in the Network

The taks of the Team will be the design, synthesis and characterization of new ligands of the type N-N, N-O-N and N-C-N with and without chiral entities and palladium compounds thereof. New ligands and complexes will be shared with groups involved in reactions not studied in Amsterdam. Mechanistic studies and in particular high pressure NMR and 15N NMR (in situ) studies of the copolymerization and alcoxycarbonylation reactions will be carried out. All studies in collaboration with guest-researchers from the Network .Coordinate training of Young Researchers in high pressure NMR and NMR of heteronuclei.

Team TU/e

Prof. Dr. Piet van Leeuwen

Management Team
Eindhoven University of Technology
Laboratory of Inorganic Chemistry and Catalysis
Den Dolech 2
5612 AZ Eindhoven The Netherlands
phone: +31 40 2473040
Fax: +31 40 2444321


Specific action in the Network

The tasks of the team will be the design and the synthesis of new ligands of the type P-O-P, N-O-N and X-P, the synthesis and characterization of new complexes, sharing those new ligands and complexes with groups involved in reactions not studied in Eindhoven, determination of ligand properties, in situ studies focussing on HP-IR, the study of the amidocarbonylation using own ligands and those prepared elsewhere in the Network, the study of insertion of imines in catalytic systems, carry out kinetic studies of selected systems in collaboration with guest-researchers fron the Network. Coordinate training of Young Researchers in Industry.


Dr. Andrea Meli

Consiglio Nazionale delle Ricerche
Istituto di Chimica dei Composti Organometallici
Via Madonna del Piano
50019 Sesto Fiorentino (Firenze) Italy
phone: +39 055 5225285
Fax: +39 055 5225203


Specific action in the Network

  • Design and synthesis of bidentate ligands containing nitrogen and /or phopshorus donor atoms with various skeletons and susbtituents. Preparation and characterization of new palladium and nickel catalyst precursors for: - Copolymerization of CO and ethylene and/or alpha or polar olefins into polyketonic materials in different phase-variation systems; - Alkoxycarbonylation of alpha-olefins; - Mechanistic studies of the catalytic reactions by means of in situ high-pressure NMR spectroscopy and the determination of the kinetics by means of spectroscopic and gas-absorption techniques.

Team ULP

Dr. Pierre Braunstein

Universitè Luis Pasteur Strasbourg I
Laboratoire de Chimie de Coordination
Rue Blaise Pascal 4
67070 Strasbourg France
phone: +33 3 90241308
Fax: +33 3 90241322


Specific action in the Network

  • Synthesis of new bi- and tridentate functional phopshine ligands with N or O donor atoms, in particular with oxazoline moieties, for the geometrical and stereochemical control of the coordination sphere of late transition metals, in particular of Ni, Pd and Pt; - Design of the hicral versions of the ligands where appropriate; - Co-polymerization of CO/norbornadiene, CO/norbornadiene/polar olefins; - CO/alpha-olefins and VO/alpha-olefins/polar olefins; - Catalytic hydrogen transfer reactions of 2-propanol to ketones and polyketones using novel ruhtenium catalysts.

Team URV

Prof. Dr. Carmen Claver

Universitat Rovira I Virgili
Department de Quimica Fisica i Inorganica
Plaça Imperial Tarraco 1
43005 Tarragona Spain
phone: +34 977 559574
Fax: +34 977 559563


Specific action in the Network

  • Development of synthetic routes for the preparation of complexes of Pd(II) containing P ligands to be used as catalytic precursors in alcoxycarbonylation; use of chiral ligands focusing on the enantioselective version of this reaction; - Design of C2 and no C2 chiral ligands with systematic modifications; use of N-N ligands in the palladium co-polymerization of CO/styrene. Relation between the electronic and steric properties of the catalyst and the obtained products; - Mechanistic studies, characterization of intermediates and kinetic studies of the reactions.


Prof. Giambattista Consiglio

Laboratorium für Technische Chemie

8093 Zürich Switzerland

phone: +41 1 6323552
Fax: +41 1 6321162


Specific action in the Network

The Zurich Team will provide new catalytic systems, which due to activity, regio- and stereoselectivity will be worth of further studies: - Synthesis of meso- and optically active homologues of 1,2-bis(diphenyl-phosphino)methyl]benzene and of the corresponding palladium complexes; - Copolymerization of CO and aliphatic 1-olefins; - Synthesis of meso- and optically active bis(oxazoline) ligands and of atropoisomeric P-N ligands and of the corresponding palladium complexes; - Copolymerization of CO and aromatic 1-olefins and terpolymerization with ethene.


15/Dec/2006 - Crevatin