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NEW HOMOGENEOUS CATALYSTS FOR OXIDATION REACTIONS WITH HYDROGEN PEROXIDE OR MOLECULAR OXYGEN AS OXIDANTS

Objetivo


Metalloporphyrin and oxometalloporphyrins containing the elements aluminium, platinum, titanium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, rhenium, ruthenium, osmium and arsenic have been synthesised and characterised. The porphyrin complexes of these metals were tested as epoxidation catalysts by use of a screening procedure. The nonmetallic elements selenium and tellurium could not be introduced into the porphyrin system. No activity was found with the porphyrin complexes of aluminium and platinum, and those of titanium, vanadium and osmium were only of minor activity. Niobium, tantalum and arsenic derivatives showed some activity, and the molybdenum, tungsten and rhenium derivatives the most promising activity.

Significant improvements in the syntheses of the porphyrin complexes of niobium, tantalum, arsenic, molybdenum, tungsten and rhenium were made. The large scale syntheses of molybdenum, tungsten and rhenium porphyrins were achieved, and complexes of these metals with porphyrin ligands of a more refined nature, especially of water soluble were synthesised. A hitherto unknown unstable reaction product of oxotungsten(V) porphyrins with hydrogen peroxide was detected.

New metalloporphyrins and transition metal bases were developed as selective homogeneous catalysts for epoxidation of olefins with hydrogen peroxide.

Electrophilicty was increased by means of novel oxomolybdenum (v), oxotungsten (v) and oxorhenium (v) porphyrin catalysts for which efficient large scale syntheses were developed, in experiments using both aqueous and anhydrous hydrogen peroxide solutions.

Nucleophilicity was increased by optimizing the catalytic behaviour of P2PtCF3X catalysts. This proved the most advantageous process studied because of the compatibility of the platinum catalysts with all grades of hydrogen peroxide.
HYDROGEN PEROXIDE IS AN ATTRACTIVE OXIDANT FROM THE STANDPOINT OF COST, AND BECAUSE WATER IS ITS ONLY REDUCTION PRODUCT NEW CATALYTIC OXIDATION SYSTEMS SHOULD ACHIEVE AN INCREASING IMPORTANCE COMPARED TO MORE CONVENTIONAL OXIDANTS.
THE OBJECTIVE OF THE PROGRAMME WAS THE DEVELOPMENT OF SELECTIVE HOMOGENEOUS OXIDATION CATALYSTS FOR REACTIONS (EPOXIDATION, HYDROXYLATION OF PHENOLS) WITH HYDROGEN PEROXIDE AS OXIDANT WHICH IN TURN IMPROVE ITS REACTIVITY, I.E. INCREASE EITHER THE ELECTROPHILICITY OR THE NUCLEOPHILICITY OF HYDROGEN PEROXIDE.

Tema(s)

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Convocatoria de propuestas

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Régimen de financiación

CSC - Cost-sharing contracts

Coordinador

DEGUSSA AG
Aportación de la UE
Sin datos
Dirección
Benningsenplatz 1
40474 DUESSELDORF
Alemania

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Coste total
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Participantes (3)