电喷雾质谱中过渡金属离子诱导的有机化合物的裂解反应及其规律研究

Electrospray ionization mass spectrometry (ESI-MS) is an important analytical tool. Fragmentation rules of organic compounds in the ESI-MS are quite insufficient, which has restricted the further applications of ESI-MS in the field of organic chemistry. Proton and metal ion adducts are two important kinds of quasi-molecular ions in ESI-MS, which can provide molecular weight information. In recent years, researches on the fragmentation of protonated ions have received tremendous attention, however, it pays little attention to the transition metal ion-induced fragmentation reactions. The studies on the fragmentation of transition metal ion adducts are not comprehensive or in-depth, and the applicable fragmentation rules are scarce. In view of this, this project intends to conduct in-depth investigation on the fragmentation behavior of multi-class model compounds' transition metal ion adducts in ESI-MS. We try to clarify the mechanism of transition metal ion-induced fragmentation reaction through analyzing the special fragments, identifying characteristic structure-fragment relationship. Studying the fragmentation of transition metal ion-adducted organic molecules under gas-phase and solvent-free conditions also helps to explore the intrinsic mechanism of transition metal activated chemical bond breaking and reveal the structure and reactivity of some novel organometallic reactive intermediates. Such research can provide key evidence for the related organometallic reactions. After summarizing a series of model organic compounds' fragmentation reaction rules, we try to establish a new mass spectrometric method for structure identification based on transition metal ion-induced fragmentation reactions.

电喷雾质谱是当今重要的分析工具之一。目前有机化合物在电喷雾质谱中的裂解规律较为匮乏，已经制约电喷雾质谱在有机化学研究领域的更加广泛与深入的应用。质子和金属离子加合物是电喷雾质谱提供样品分子量信息的最重要的两类准分子离子，近年来质子化离子的裂解规律研究得到了广泛关注，然而对过渡金属离子诱导的裂解反应则关注较少，研究不够深入，可应用的裂解反应规律更加欠缺。鉴此，本项目拟对多类模型化合物的过渡金属离子加合物在电喷雾质谱中的裂解行为进行深入考察，分析特殊碎片，提取特征信息，阐明碎裂反应的机理， 并通过气相无溶剂条件下对过渡金属与有机分子形成的配合物的裂解反应研究，探讨过渡金属活化化学键断裂的内在机理，揭示一些新颖的金属有机活性中间体的结构及性质，为相关金属有机化学反应研究提供关键证据；在总结一系列模型有机化合物裂解反应规律的基础上，建立基于过渡金属离子诱导的裂解反应规律的质谱结构鉴定新方法。

电喷雾质谱是当今重要的分析工具之一。目前有机化合物在电喷雾质谱中的裂解规律较为匮乏，这已制约电喷雾质谱在有机化学研究领域的更加广泛与深入的应用。质子和金属离子加合物是电喷雾质谱提供样品分子量信息的最重要的两类准分子离子，近年来质子化离子的裂解规律研究得到了广泛关注，然而对过渡金属离子诱导的裂解反应则关注较少，研究不够深入，可应用的裂解反应规律更加欠缺。鉴此，本项目对多类模型化合物的过渡金属离子加合物在电喷雾质谱中的裂解行为开展了深入考察，通过分析特殊碎片，提取富含结构特征的信息，阐明碎裂反应的机理， 并通过气相无溶剂条件下对过渡金属与有机分子形成的配合物的裂解反应研究，探讨了过渡金属活化化学键断裂的内在机理，揭示一些新颖的金属有机活性中间体的结构及性质，为相关金属有机化学反应研究提供关键证据；项目总结了一系列模型有机化合物裂解反应规律，并在此基础上建立了过渡金属离子诱导的裂解反应规律的质谱结构鉴定新方法。