Applications of new complexes of platinum group metals (Rh,Ru,Ir) as potential catalyst precursors for stereo- and enantioselective organic reactions

Projektinformationen

ID Finanzhilfevereinbarung: INTAS-94-0541

Projekt abgeschlossen

Startdatum 1 Januar 1995

Enddatum 31 Dezember 1997

Finanziert unter

• International Association for the promotion of cooperation with scientists from the independent states of the former Soviet Union (INTAS), 1993-

Gesamtkosten

Keine Daten

EU-Beitrag

€ 50 000,00

Koordiniert durch

Université de Liège
Belgium

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Verwertbare Ergebnisse

Applications of new complexes of platinum group metals (Rh, Ru, Ir) as potential catalyst precursors for stereo- and enantioselective organic reactions

A number of new organometallic complexes were synthesised including: ruthenium-carbene complexes, ruthenium complexes containing diamine-based ligands, ruthenium- and osmium-carborane complexes, rhodium-carborane complexes. Complexes were then screened for potential catalytic activity regarding olefin cyclopropanation and olefin metathesis. Ruthenium exo-mono-phosphino-7,8-dicarba-nido-undecaborate complexes were shown to be efficient catalysts for the cyclopropanation of activated olefins. A set of rhodium(I)-based catalysts were found to be effective for cyclopropanation of olefins with diazoacetates. However, they need higher temperatures and do not offer improved selectivity over other compounds. Platinum complexes were also investigated. Cometathesis reactions of cycloolefins with alpha-olefins in the presence of molybdenum-based catalyst systems were studied. It was shown that preferred formation of homo- or cometathesis products as well as chain propagation and termination products depend on the size of the cycloolefin ring. Two alkoxyalkenylcarbene Ru(II) complexes were synthesised as possible catalysts in ring-opening metathesis polymerisation of norbornene. Complexes were inactive at room temperature but gave yields of 26.5% at 95C. The question remains open as to what active centres exist during the reaction.