Wasserbasierte Metallkomplex-Katalysatoren. Teilprojekt: Homogenkatalyse im Zweiphasensystem - Synthese wasserloeslicher Phosphane mit massgeschneiderter Struktur Schlussbericht

Abstract

The synthetic methodology for water soluble phosphines was only poorly developed at the beginning of this project. The methods reported in the literature so far were not sufficient for a systematic approach to ligands of this type with novel structural features. Using different and complementary synthetic procedures developed by us novel types of anionic phosphines with sulfonated, carboxylated and phosphonated phenyl moieties as well as cationic types of ligands with ammonium and guanidinium substituents in their peripheries were obtained. In addition to nucleophilic phosphination of sulfonated, carboxylated and phosphonated fluorobenzene derivatives, Pd-catalyzed P-C coupling of primary and secondary phosphines with iodo- or bromobenzene derivatives bearing polar substituents could be established as a novel synthetic method of broad applicability. The structures of water soluble phosphine ligands and their complexes have been obtained by X-ray structural analysis which provided useful parameters for quantum mechanical calculations and molecular modeling of catalyst structures. p-TPPTS, m-TPPTS and guanidinium phosphines have been evaluated as catalyst ligands in Rh-catalyzed hydroformylation of n-hexene in two-phase systems. In various Pd-catalysed C-C-coupling reactions in aqueous media guanidinium phosphines proved to be of surmounting activity. (orig.)SIGLEAvailable from TIB Hannover: DtF QN1(55,3) / FIZ - Fachinformationszzentrum Karlsruhe / TIB - Technische InformationsbibliothekBundesministerium fuer Bildung, Wissenschaft, Forschung und Technologie, Bonn (Germany)DEGerman