Infrared Ion Spectroscopy for the Gas-Phase Characterization of Organo- and Biocatalysis Intermediates

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The study of reactive intermediates lies at the heart of catalysis research and development. The applicants are intending to join forces (AB: synthetic organic chemistry and catalysis; MS: mass spectrometry and infrared ion spectroscopy) to investigate, in the gas-phase, the generation, structure and reactivity of two centrally important intermediates in organo- and biocatalysis: (A) the so-called Breslow intermediates of carbene-based Umpolung, and (B) hydroxycarbenes. For the Breslow intermediates, it is hoped that a thorough understanding of their reactivity-determining keto-enol tautomerism will be achieved. Additionally, their reactivity, e.g. towards carbonyl acceptors, other electrophiles and metal complex fragments will be probed in detail in the gas-phase. Hydroxycarbenes are mechanistically related to Breslow intermediates, as they can be considered as umpoled aldehyde tautomers, and shall be investigated analogous to the Breslow intermediates. Additionally, they are hoped to serve as vehicles for the in-depth study of the kinetics/structural requirements for hydrogen tunneling processes in the gas-phase.