Fluorosilane Activation by Pd/Ni→Si-F→Lewis Acid Interaction: An Entry to Catalytic Sila-Negishi Coupling
Fluorosilane Activation by Pd/Ni→Si-F→Lewis Acid Interaction: An Entry to Catalytic Sila-Negishi Coupling
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DOI：
10.1021/jacs.0c04690
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发表时间：
2020-08-19
影响因子：
15
通讯作者：
Bourissou, Didier
中科院分区：
文献类型：
--
作者：
Kameo, Hajime;Yamamoto, Hiroki;Bourissou, Didier
公开了一种涉及M -> Z相互作用的键活化的新模式。作为σ-受体配体的过渡金属的配位被发现使氟硅烷的活化成为可能，为第一过渡金属催化的Si-F键活化开辟了道路。使用膦作为导向基团，通过将Pd和Ni配合物与外部刘易斯酸如MgBr 2组合来开发硅-根岸偶联。几个关键的催化中间体已经通过光谱学和晶体学鉴定。结合DFT计算，所有数据支持通过Pd/Ni -> Si-F ->刘易斯酸相互作用的氟硅烷的协同活化，Z-型氟硅烷配体转化为X-型甲硅烷基部分。
A new mode of bond activation involving M -> Z interactions is disclosed. Coordination to transition metals as sigma-acceptor ligands was found to enable the activation of fluorosilanes, opening the way to the first transition-metal-catalyzed Si-F bond activation. Using phosphines as directing groups, sila-Negishi couplings were developed by combining Pd and Ni complexes with external Lewis acids such as MgBr2. Several key catalytic intermediates have been authenticated spectroscopically and crystallographically. Combined with DFT calculations, all data support cooperative activation of the fluorosilane via Pd/Ni -> Si-F -> Lewis acid interaction with conversion of the Z-type fluorosilane ligand into an X-type silyl moiety.