Carpenter Stephanie H, Neidig Michael L
Department of Chemistry, University of Rochester, Rochester, New York 14627 (USA), Tel: 585-276-6006.
Isr J Chem. 2017 Dec;57(12):1106-1116. doi: 10.1002/ijch.201700036. Epub 2017 Aug 24.
Detailed studies of iron speciation and mechanism in iron-catalyzed cross-coupling reactions are critical for providing the necessary fundamental insight to drive new reaction development. However, such insight is challenging to obtain due to the prevalence of mixtures of unstable, paramagnetic organoiron species that can form in this chemistry. A physical-inorganic research approach combining freeze-trapped inorganic spectroscopic studies, organometallic synthesis and GC/kinetic studies provides a powerful method for studying such systems. Mössbauer, EPR and MCD spectroscopy enable the direct investigation of formed iron species and, combined with GC analysis, the direct correlation of reactions of specific iron species to the generation of organic products. This review focuses on a description of the key methods involved in this physical-inorganic approach, as well as examples of its application to investigations of iron-SciOPP catalyzed cross-coupling catalysis.
详细研究铁催化交叉偶联反应中的铁形态和机理，对于提供必要的基础认识以推动新反应的开发至关重要。然而，由于在这种化学过程中会形成不稳定的顺磁性有机铁物种混合物，因此很难获得这样的认识。结合冷冻捕集无机光谱研究、有机金属合成和气相色谱/动力学研究的物理无机研究方法，为研究此类体系提供了一种强大的方法。穆斯堡尔光谱、电子顺磁共振光谱和磁圆二色光谱能够直接研究生成的铁物种，并且与气相色谱分析相结合，可以将特定铁物种的反应与有机产物的生成直接关联起来。本综述重点描述了这种物理无机方法所涉及的关键方法，以及其在铁-科学有机膦催化交叉偶联催化研究中的应用实例。
