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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.
Objectives
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:
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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.
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Similar
catalysis to get oligomers, which, after modification, function
as resins. Control of molecular weight and composition is an issue.
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The
amidocarbonylation reaction, which makes directly amino acids from
small molecules. Enantioselectivity is a key issue.
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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:
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evaluation
of the catalytic activity of the new complexes toward co-
and ter-polymerization reactions, oligomerisation and carbonylation
reactions;
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identification
and characterization of the products, including
molecular weight distribution of polymers;
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investigation
of the catalytic cycle;
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identification
by in situ studies of the catalytic intermediates and
resting states;
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kinetic
modelling;
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molecular
modelling.
Training
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:
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Team
UNITS : homogeneous catalysis,
high-pressure reactions, X-ray structural characterization by means of
synchrotron radiation, chemical systems based on Nitrogen ligands;
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Team
UAMSK : high tech and high pressure
NMR, non traditional solvents (sc CO 2),
chemical systems
based on Nitrogen ligands;
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Team TU/e
: in situ studies of
catalysts, kinetics, molecular modelling, chemical systems based on
Phosphorus ligands;
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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);
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Team ULP
: homogeneous catalysis,
synthesis of chiral igands, chemical systems based on hemilabile P-N
and P-O ligands;
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Team URV
: synthesis of chiral ligands,
homogeneous catalysis, high pressure NMR, in situ studies of catalysts,
non traditional solvents (sc CO 2 );
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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.
Participants
Team UNITS
Prof. Giovanni Mestroni
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Network
Coordinator
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Università di
Trieste
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Dipartimento
di Scienze
Chimiche
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Via Licio
Giorgieri 1
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34127
Trieste Italy
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phone: +39 040
5583956
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Fax:
+39 040 5583903
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Specific
action in the Network
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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.
Team UAMSK
Prof. Dr. Kees Elsevier
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Universiteit
van Amsterdam
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Institute of
Molecular Chemistry
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Nieuwe
Achtergracht 166
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1018 WV
Amsterdam The Netherlands
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phone: +31 20
5255653
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Fax: +31 20
5255653
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e-mail: else@science.uva.nl
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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
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.
Team
CNR.ICCOM
Dr.
Andrea Meli
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Consiglio
Nazionale delle
Ricerche
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Istituto
di Chimica dei
Composti Organometallici
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Via
Madonna del Piano
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50019
Sesto Fiorentino
(Firenze) Italy
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phone:
+39 055 5225285
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Fax:
+39 055 5225203
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e-mail: andrea.meli@iccom.cnr.it
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Specific
action in the Network
Team ULP
Specific
action in the Network
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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
Specific
action in the Network
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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.
Team ETHZ
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.
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