The Rise of Iron: Progress in Iron-Based Metal Catalyzed Hydrosilylation of Olefins

The hydrosilylation reaction of olefins refers to the reaction in which silicon groups and hydrogen atoms in silanes are respectively added to both ends of the carbon-carbon double bond of olefins to form alkylsilanes. Transition metal-catalyzed hydrosilation of olefins and tertiary silanes has become one of the most important and basic homogeneous catalytic reactions in industry. The silicone products produced are widely used in daily necessities such as textiles and filler surface treatment agents, cosmetics and low-resistance tire additives, sealants, adhesives and release agents, and are an indispensable class of chemicals.

Since the discovery of the hydrosilylation reaction of olefins, a series of transition metal catalysts have been developed successively, which have effectively improved the efficiency and selectivity of the hydrosilylation reaction of olefins. However, the catalysts used in the industrial production of organosilicon are still mainly based on noble metal platinum catalysts, and the extensive use of platinum catalysts does not meet the requirements of sustainable development chemistry. Therefore, the development of green and cheap iron-based metal-catalyzed hydrosilation of olefins is of great research significance, and has become a hot research field, and a series of important progress has been made.

Recently, the research group of Zhu Shoufei from Nankai University reviewed the research progress of iron-based metal-catalyzed hydrosilylation reactions of olefins and tertiary silanes. According to the classification of metals, the author systematically sorted out the research progress of the hydrosilylation reaction of olefins and tertiary silanes catalyzed by three iron-based metals: iron, cobalt and nickel. Iron-based metal-catalyzed hydrosilation of olefins and tertiary silanes has made a lot of progress. The use of redox-active ligands helps to form open-shell metal catalysts, which is beneficial to obtain high activity and selectivity; the optimization of the activation mode makes the operation of the corresponding catalytic reaction easier, and in some cases, it also plays a key role in improving the functional group tolerance and stability of the catalyst. It should be pointed out that iron-based metal catalysts that can truly compete with platinum catalysts in activity, selectivity, and tolerance to water, oxygen and other conditions have not yet appeared, and there is still a long way to go for the practical application of iron-based metal catalysts in the organosilicon industry. In view of the current challenges in this field, the author believes that continuing to develop different types of ligand-modified iron-based metal catalysts, and exploring the influence of activating reagents, anions, and additives on the stability, activity and selectivity of iron-based metal catalysts is undoubtedly still the main task in this field. On the other hand, summarizing the law of the reaction of olefins and tertiary silanes catalyzed by iron-based metals, in-depth study of the mechanism of these reactions, and revealing the structure-activity relationship of catalysts will further improve people’s rational design ability and level in this field. At the same time, it will also provide reference and inspiration for other reactions catalyzed by iron group metals.