Ulrich Hintermair

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Rapid hydroformylation of 1-octene (rates up to 800 h(-1)) with the catalyst remaining stable for at least 40 h and with very low rhodium leaching levels (0.5 ppm) is demonstrated when using a system involving flowing the substrate, reacting gases and products dissolved in supercritical CO(2) (scCO(2)) over a fixed bed supported ionic liquid phase catalyst.
Molecular catalysts are known for their high activity and tunability, but their solubility and limited stability often restrict their use in practical applications. Here we describe how a molecular iridium catalyst for water oxidation directly and robustly binds to oxide surfaces without the need for any external stimulus or additional linking groups. On(More)
Organometallic iridium complexes bearing oxidatively stable chelate ligands are precursors for efficient homogeneous water-oxidation catalysts (WOCs), but their activity in oxygen evolution has so far been studied almost exclusively with sacrificial chemical oxidants. In this report, we study the electrochemical activation of Cp*Ir complexes and demonstrate(More)
We present evidence for Cp* being a sacrificial placeholder ligand in the [Cp*Ir(III)(chelate)X] series of homogeneous oxidation catalysts. UV-vis and (1)H NMR profiles as well as MALDI-MS data show a rapid and irreversible loss of the Cp* ligand under reaction conditions, which likely proceeds through an intramolecular inner-sphere oxidation pathway(More)
Real-time monitoring of light scattering and UV-vis profiles of four different Cp*Ir(III) precursors under various conditions give insight into nanoparticle formation during oxidation catalysis with NaIO(4) as primary oxidant. Complexes bearing chelate ligands such as 2,2'-bipyridine, 2-phenylpyridine, or 2-(2'-pyridyl)-2-propanolate were found to be highly(More)
Organometallic catalysis is a powerful tool for chemical synthesis, and the field still evolves at a high pace continuously improving efficiencies and opening up new possibilities. However, despite increasing use in specialty and fine chemical production issues of catalyst recovery still hamper broader application and prevent tapping the full potential of(More)
A supported ionic liquid phase (SILP) catalyst prepared from [PrMIM][Ph(2)P(3-C(6)H(4)SO(3))] (PrMIM = 1-propyl-3-methylimidazolium), [Rh(CO)(2)(acac)] (acacH = 2,4-pentanedione) [OctMIM]NTf(2) (OctMIM = 1-n-octyl-3-methylimidazolium, Tf = CF(3)SO(2)) and microporous silica has been used for the continuous flow hydroformylation of 1-octene in the presence(More)
Dual role for CO(2): Pure formic acid can be obtained continuously by hydrogenation of CO(2) in a single processing unit. An immobilized ruthenium organometallic catalyst and a nonvolatile base in an ionic liquid (IL) are combined with supercritical CO(2) as both reactant and extractive phase.
A series of Cp*Ir(III) dimers have been synthesized to elucidate the mechanistic viability of radical oxo-coupling pathways in iridium-catalyzed O2 evolution. The oxidative stability of the precursors toward nanoparticle formation and their oxygen evolution activity have been investigated and compared to suitable monomeric analogues. We found that(More)
FlowNMR spectroscopy is an excellent technique for non-invasive real-time reaction monitoring under relevant conditions that avoids many of the limitations that bedevil other reaction monitoring techniques. With the recent commercial availability of FlowNMR hardand software solutions for high resolution spectrometers it is enjoying increased popularity in(More)