Sie befinden Sich nicht im Netzwerk der Universität Paderborn. Der Zugriff auf elektronische Ressourcen ist gegebenenfalls nur via VPN oder Shibboleth (DFN-AAI) möglich. mehr Informationen...
[Display omitted]
•Acyliridium complexes from furfurylamine have been prepared and fully characterised.•Solvent choice allows preferred formation of diverse diacyl or ketoimine structures.•All are homogeneous pre-catalysts for hydrolysis of amineboranes releasing hydrogen.
The irida-β-diketone [IrHCl{(PPh2(o-C6H4CO))2H}] (1) reacts with furfurylamine to afford different products depending on the solvent used. When the reaction is carried out in a THF/H2O mixture [IrH(PPh2(o-C6H4CO))2(NH2(CH2)C4H3O-κN)] (2) is obtained via dehydrodechlorination and amine-coordination of the ligand. Upon addition of furfurylamine to 1 in methanol, a dehydrogenation reaction leads to [IrCl(PPh2(o-C6H4CO))2(NH2(CH2)C4H3O-κN)] (3). When the reaction takes place in dry THF a Schiff-base reaction occurs yielding a hydridoirida-β-ketoimine derivative [IrH(PPh2(o-C6H4CO)(PPh2(o-C6H4CN(CH2)C4H3O))] (4). All three complexes have been fully NMR characterised and also by single-crystal X-ray diffraction. They have been tested as homogeneous catalysts on the hydrolysis of amine-borane adducts. Complex 2 shows the best results, releasing all 3 equivalents of hydrogen. In situ NMR experiments have been carried out to allow the observation of catalytic intermediates.