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开发的核心。申请者打算联合起来(AB：合成有机化学和催化；MS：质谱学和红外离子光谱)，在气相中研究有机和生物催化中两个核心重要中间体的生成、结构和反应活性：(A)所谓的基于卡宾的Umpolung的Breslow中间体，以及(B)羟基卡宾。对于Breslow中间体，希望能够彻底了解它们的反应性决定酮烯醇互变异构体。此外，将在气相中详细探讨它们的反应性，例如对羰基受体、其他亲电剂和金属络合物碎片的反应性。羟卡宾在力学上与Breslow中间体有关，因为它们可以被认为是无极化醛互变异构体，应类似于Breslow中间体进行研究。此外，它们有望成为深入研究气相中氢隧道过程的动力学/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.