Transition-metal-catalyzed alkene hydrosilylation is one of the most important homogeneous catalytic reactions, and the development of methods that use base metals, especially iron, as catalysts for this transformation is a growing area of research. However, the limited number of ligand scaffolds applicable for base-metal-catalyzed alkene hydrosilylation has seriously hindered advances in this area. Herein, we report the use of 1,10-phenanthroline ligands in base-metal catalysts for alkene hydrosilylation. In particular, iron catalysts with 2,9-diaryl-1,10-phenanthroline ligands exhibit unexpected reactivity and selectivity for hydrosilylation of alkenes, including unique benzylic selectivity with internal alkenes, Markovnikov selectivity with terminal styrenes and 1,3-dienes, and excellent activity toward aliphatic terminal alkenes. According to the mechanistic studies, the unusual benzylic selectivity of this hydrosilylation initiates from π-π interaction between the phenyl of the alkene and the phenanthroline of the ligand. This ligand scaffold and its unique catalytic model will open possibilities for base-metal-catalyzed hydrosilylation reactions.

中文翻译：

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具有1,10-菲咯啉骨架的配体，用于高度区域选择性的铁催化的烯烃氢化硅烷化。

过渡金属催化的烯烃氢化硅烷化是最重要的均相催化反应之一，使用贱金属（特别是铁）作为该转化催化剂的方法的开发是一个不断发展的研究领域。然而，可用于贱金属催化的烯烃氢化硅烷化的配体支架数量有限，严重阻碍了该领域的发展。本文中，我们报道了在贱金属催化剂中使用1,10-菲咯啉配体进行烯烃氢化硅烷化。特别地，具有2,9-二芳基-1,10-菲咯啉配体的铁催化剂表现出出乎意料的反应性和烯烃氢化硅烷化的选择性，包​​括与内部烯烃的独特苄基选择性，与末端苯乙烯和1,3-二烯的马尔可夫尼科夫选择性，以及出色的对脂族末端烯烃的活性。根据机理研究，这种氢化硅烷化的不同的苄基选择性是由烯烃的苯基与配体的菲咯啉之间的π-π相互作用引发的。这种配体支架及其独特的催化模型将为贱金属催化的氢化硅烷化反应打开可能性。