Structure-Reactivity Studies of Intermediates for Mechanistic Information by Subensemble Fluorescence Microscopy
Structure-Reactivity Studies of Intermediates for Mechanistic Information by Subensemble Fluorescence Microscopy
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DOI：
10.1021/acscatal.7b00627
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发表时间：
2017-06-01
期刊：
影响因子：
12.9
通讯作者：
Blum, Suzanne A.
中科院分区：
文献类型：
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作者：
Kitagawa, Kazuhiro;Blum, Suzanne A.
有机金属配合物的结构-反应性研究在帮助有机金属和合成有机化学中基于机理的反应设计方面有着丰富的历史。最初由物理有机化学家开发，后来被新兴的有机金属化学领域采用，1分子水平的结构反应性研究提供了将金属络合物和底物结构变化相关联的能力（例如，通过配体设计，电子参数，底物结构，溶剂配位等）。单个步骤或整个反应的反应性变化。然后，这种能力被用来创建预测模型，用于开发新的反应;将化学扩展到新的底物;以及改善催化活性、选择性或其他期望的反应性质。然而，这种结构-反应性研究常常受到活性中间体数量少的阻碍，特别是当涉及有机金属中间体时。这些中间体可能不会积累到传统的整体分析技术检测所需的数量。1这种总体技术最适合于识别混合物中的主要成分;然而，这些反应性成分往往不是主要成分。1这种差异导致在实地长期存在的分析挑战。因此，结构-反应性研究有时不能通过直接检测特定的中间体来进行，而是必须通过测量对整个反应的影响来间接梳理。在这些情况下，很难确定具体中间体的反应性变化，而不是整个反应的变化。这种困难阻碍了预测反应模型的发展，从而反应设计和improvement.Driven需要识别和研究有限数量的有机金属物种的条件下，相关的催化剂，合成有机，制备有机金属化学，我们的实验室和金匠实验室最近报道了两个亚系综荧光显微镜方法来解决这个问题（图1）。2− 4次荧光
Structure− reactivity studies of organometallic complexes have a rich history in aiding mechanism-based reaction design in organometallic and synthetic organic chemistry. Originally developed by physical-organic chemists and later adopted for the emerging field of organometallic chemistry, 1 structure− reactivity studies at the molecular level provide the ability to correlate changes in the structure of metal complexes and substrates (eg, through ligand design, electronic parameters, substrate structure, solvent coordination, etc.) to changes in reactivity of individual steps or in the reaction overall. This ability is then employed to create predictive models for development of new reactions; extension of the chemistry to new substrates; and improvement of catalytic activity, selectivity, or other desirable reaction properties. Often such structure− reactivity studies, however, are hampered by a low quantity of reactive intermediates, especially when organometallic intermediates are involved. These intermediates might not build up to the quantity needed for detection by traditional ensemble analytical techniques. 1 Such ensemble techniques are best-suited to identifying the major components in mixtures; yet, often these reactive components are not the major components. 1 This discrepancy leads to long-standing analytical challenges in the field. Thus, structure− reactivity studies are sometimes unable to be performed through direct detection of specific intermediates and instead must be teased out indirectly through measurement of the effects on the overall reaction. In these cases the changes in reactivity of specific intermediates rather than changes in the reaction overall are difficult to assign. This difficulty hinders predictive reaction model development and thus reaction design and improvement.Driven by the need to identify and study limited quantities of organometallic species under conditions relevant to catalysts, synthetic organic, and preparative organometallic chemistry, our laboratory and the Goldsmith laboratory have recently reported two subensemble fluorescence microscopy approaches to this problem (Figure 1). 2− 4 Subensemble fluorescence