Transition-Metal-Mediated Germanium–Fluorine Activation: Inverse Electron Flow in σ-Bond Metathesis

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• 作者：Hajime Kameo ; Koki Ikeda ; Didier Bourissou ; Shigeyoshi Sakaki ; Shin Takemoto ; Hiroshi Nakazawa ; Hiroyuki Matsuzaka
• 刊名：Organometallics
• 出版年：2016
• 出版时间：March 14, 2016
• 年：2016
• 卷：35
• 期：5
• 页码：713-719
• 全文大小：442K
• ISSN：1520-6041

文摘

We report the first example of Ge–F activation using a transition metal complex, in which σ-bond metathesis between Ge–F and Ir–H σ-bonds takes place with a specific electron flow. Unexpected selectivity for Ge–F over Ge–C_Ph σ-bond activation is observed. Density functional theory suggests that a strong dative Ir→Ge interaction, which efficiently weakens the σ-bond, helps electrostatically the coupling between the (δ−) fluorine on Ge and the (δ+) hydrogen on Ir, making Ge–F bond activation very easy.