High-resolution electrospray-ionization tandem-mass spectrometer

电喷雾电离（ESI）质谱是鉴定化学转化反应和催化中间体的最有效的分析方法之一。特别是，它对于有机金属物种的分析具有重要价值，因为它能够区分金属中心的不同聚集，缔合和配位状态，即使在溶液中发生快速动态平衡。最近的例子也表明，时间分辨ESI质谱实验可以提供深入的动力学信息。最后，串联质谱仪提供了检查质量选择离子的微观单分子反应性的可能性。以这种方式，可以探测单个基本步骤，而不受分子间交换过程或溶剂配位的干扰。因此，获得的机制的见解是至关重要的合理发展，改善实际应用。所要求的高分辨率ESI串联质谱仪将用于确定有机铜酸盐的形态，并阐明铁催化的交叉偶联以及过渡金属介导的氧化还原和C-O活化反应的机制。此外，它将被应用于广泛的聚合反应的实时分析。与此同时，所要求的仪器的串联功能将被用于检查许多过渡金属络合物的金属转移反应和还原消除。负责申请人在使用高分辨率ESI串联质谱仪进行有机金属反应的机理研究方面拥有丰富的经验，其中大部分是使用2011年委托的仪器进行的。由于频繁将含有反应性有机金属化合物的高浓度样品溶液注入该设备以及由于新一代质谱仪的开发而导致的严重磨损，现有仪器不再允许进行最先进的实验，需要尽快更换。所需的仪器将取代旧仪器，从而确保申请人及其合作伙伴能够保持其国际竞争力。此外，新仪器的上级质量分辨率将提供令人兴奋的实验可能性，远远超出旧设备的可行性。

Electrospray-ionization (ESI) mass spectrometry is one of the most powerful analytical methods for the identification of reactive and catalytic intermediates of chemical transformations. In particular, it is of great value for the analysis of organometallic species because it is able to distinguish between the different aggregation, association, and coordination states of the metal centers, even if fast dynamic equilibria occur in solution. Recent examples have also demonstrated that time-resolved ESI-mass spectrometric experiments can afford in-depth kinetic information. Finally, tandem-mass spectrometers offer the possibility to examine the microscopic unimolecular reactivity of mass-selected ions. In this way, individual elementary steps can be probed without the interference of intermolecular exchange processes or solvent coordination. The thus obtainable mechanistic insight is of key importance for the rational development of improved practical applications. The requested high-resolution ESI tandem-mass spectrometer will be used for determining the speciation of organocuprates and elucidating the mechanism of iron-catalyzed cross-coupling as well as transition-metal mediated fluorination and C–O activation reactions. Moreover, it will be applied to the real-time analysis of a wide range of polymerization reactions. At the same time, the tandem functionality of the requested instrument will be taken advantage of for examining transmetalation reactions and reductive eliminations for numerous transition-metal complexes. The applicant in charge has extensive experience in the use of high-resolution ESI tandem-mass spectrometers for mechanistic studies of organometallic reactions, most of which have been performed with an instrument commissioned in 2011. Due to the heavy wear resulting from the frequent infusion of highly concentrated sample solutions containing reactive organometallics into this device as well as due to the development of a new generation of mass spectrometers, the existing instrument no longer permits state-of-the-art experiments and needs to be replaced as soon as possible. The requested instrument will substitute the old one and, thus, ensure that the applicant and his collaboration partners can maintain their international competitiveness. Moreover, the superior mass resolution of the new instrument will offer exciting experimental possibilities far beyond those feasible with the old equipment.