Influence of structural and electronic properties of organomolybdenum(ii) complexes of the type [CpMo(CO)3R] and [CpMo(O2)(O)R] (R = Cl, CH3, CF3) on the catalytic olefin epoxidation†,10.1039/C4CY01604A

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Influence of structural and electronic properties of organomolybdenum(ii) complexes of the type [CpMo(CO)3R] and [CpMo(O2)(O)R] (R = Cl, CH3, CF3) on the catalytic olefin epoxidation†

Simone A. Hauser,Robert M. Reich,Alexander Pöthig,Mirza Cokoja

Catalysis Science & Technology Pub Date : 01/16/2015 00:00:00 , DOI:10.1039/C4CY01604A

Abstract

Six compounds of the type [CpMo(CO)₃R] (R = Cl (1), CH₃ (2), CF₃ (3)) and [CpMo(O₂)(O)R] (R = Cl (4), CH₃ (5), CF₃ (6) (Cp = η⁵-cyclopentadienyl)) have been synthesised and characterised. The crystal structures of [CpMo(CO)₃CF₃] and [CpMo(O₂)(O)CF₃] are compared to their literature known chloro and methyl derivatives. The influence of the groups R on the performance as epoxidation catalysts is examined. DFT calculations, IR-spectroscopy and X-ray crystallography help to explain differences in reactivity and enable a rational design of active molybdenum tricarbonyl and oxo-peroxo complexes.