High-resolution electrospray-ionization tandem-mass spectrometer

电喷雾电离(ESI)质谱法是鉴定化学转化的活性中间体和催化中间体的最有效的分析方法之一。特别是对于有机金属物种的分析，它具有重要的价值，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也是如此。最近的例子也表明，时间分辨ESI-MS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验质量选择离子的微观单分子反应性的可能性。通过这种方式，可以在不干扰分子间交换过程或溶剂配位的情况下探索单个基本步骤。这样获得的机械洞察力对于改进的实际应用的合理发展是至关重要的。所要求的高分辨率电喷雾串联质谱计将用于确定有机铜的形态，并阐明铁催化的交叉偶联以及过渡金属介导的氟化和C-O活化反应的机理。此外，它还将应用于各种聚合反应的实时分析。同时，所请求的仪器的串联功能将被用于研究许多过渡金属络合物的易金属反应和还原消除。主管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有丰富的经验，其中大部分是使用2011年投入使用的仪器进行的。由于频繁向该装置中注入含有活性有机金属的高浓度样品溶液造成的严重磨损，以及新一代质谱仪的开发，现有仪器不再允许进行最先进的实验，需要尽快更换。所要求的文书将取代旧文书，从而确保申请者及其合作伙伴能够保持其国际竞争力。此外，新仪器卓越的质量分辨率将提供令人兴奋的实验可能性，远远超过旧设备所能提供的可能性。

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.