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

活性中间体的研究是催化研究和发展的核心。申请人打算联合起来（AB：合成有机化学和催化；MS：质谱和红外离子光谱），在气相中研究有机和生物催化中两种重要中间体的生成、结构和反应性：(A)所谓的Breslow碳基Umpolung中间体，和(B)羟基碳烯。对于Breslow中间体，希望对其决定反应性的酮-烯醇互变异构有一个透彻的了解。此外，它们的反应性，例如对羰基受体、其他亲电试剂和金属配合物碎片的反应性，将在气相中进行详细的探讨。羟基碳烯在机理上与Breslow中间体相关，因为它们可以被认为是无极性醛互变异构体，并且应该类似于Breslow中间体进行研究。此外，它们有望作为深入研究气相氢隧穿过程动力学/结构要求的工具。

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.