Wednesday, February 11, 2015

Natural Abundance N NMR by Dynamic Nuclear Polarization: Fast Analysis of Binding Sites of a Novel Amine-Carboxyl-Linked Immobilized Dirhodium Catalyst


Gutmann, T., et al., Natural Abundance N NMR by Dynamic Nuclear Polarization: Fast Analysis of Binding Sites of a Novel Amine-Carboxyl-Linked Immobilized Dirhodium Catalyst. Chemistry, 2015: p. n/a-n/a.


A novel heterogeneous dirhodium catalyst has been synthesized. This stable catalyst is constructed from dirhodium acetate dimer (Rh2 (OAc)4 ) units, which are covalently linked to amine- and carboxyl-bifunctionalized mesoporous silica (SBA-15NH2 COOH). It shows good efficiency in catalyzing the cyclopropanation reaction of styrene and ethyl diazoacetate (EDA) forming cis- and trans-1-ethoxycarbonyl-2-phenylcyclopropane. To characterize the structure of this catalyst and to confirm the successful immobilization, heteronuclear solid-state NMR experiments have been performed. The high application potential of dynamic nuclear polarization (DNP) NMR for the analysis of binding sites in this novel catalyst is demonstrated. Signal-enhanced 13 C CP MAS and 15 N CP MAS techniques have been employed to detect different carboxyl and amine binding sites in natural abundance on a fast time scale. The interpretation of the experimental chemical shift values for different binding sites has been corroborated by quantum chemical calculations on dirhodium model complexes.