Transition-Metal-Mediated Germanium–Fluorine Activation: Inverse Electron Flow in σ-Bond Metathesis
摘要:
We report the first example of Ge-F activation using a transition metal complex, in which sigma-bond metathesis between Ge-F and Ir-H sigma-bonds takes place with a specific electron flow. Unexpected selectivity for Ge-F over Ge-CPh bond activation is observed, Density functional theory suggests that a strong dative Ir >Ge interaction, which efficiently weakens the alpha-bond) helps electrostatically the coupling between the (5) fluorine on Ge and the (delta+) hydrogen on Ir, making Ge-F bond activation very easy.
Cationic Complexes with Au→Ge Bonds – Synthesis and Carbophilic Reactivity
作者:Mohammadjavad Karimi、Elishua Litle、François P. Gabbaï†
DOI:10.1002/ijch.202200036
日期:——
transition metals with Lewis acidic main group fragments, we have decided to investigate gold complexes bearing halogermanes as Z-type ligands. Toward this end, we have synthesized complexes of general formula [(o-(Ph2P)C6H4)2(Ph)(X)GeAuCl] (X = F, Cl). Experimental and computational analyses indicate the presence of an Au→Ge interaction in both cases. Chloride abstraction reactions have also been investigated
作为我们将后过渡金属与路易斯酸性主基团片段连接起来的努力的一部分,我们决定研究带有卤锗烷作为 Z 型配体的金配合物。为此,我们合成了通式[( o -(Ph 2 P)C 6 H 4 ) 2 (Ph)(X)GeAuCl] (X = F, Cl)的配合物。实验和计算分析表明在这两种情况下都存在 Au→Ge 相互作用。还研究了氯化物夺取反应。在 X = Cl 的情况下,用 AgSbF 6提取双氯化物提供了一种假定的指示,逐渐从其反离子中提取氟化物。在炔氢胺化反应中,这种推定的双阳离子作为催化剂也比其单阳离子类似物更具活性。
Transition-Metal-Mediated Germanium–Fluorine Activation: Inverse Electron Flow in σ-Bond Metathesis
We report the first example of Ge-F activation using a transition metal complex, in which sigma-bond metathesis between Ge-F and Ir-H sigma-bonds takes place with a specific electron flow. Unexpected selectivity for Ge-F over Ge-CPh bond activation is observed, Density functional theory suggests that a strong dative Ir >Ge interaction, which efficiently weakens the alpha-bond) helps electrostatically the coupling between the (5) fluorine on Ge and the (delta+) hydrogen on Ir, making Ge-F bond activation very easy.
Pd/Ni-Catalyzed Germa-Suzuki coupling <i>via</i> dual Ge–F bond activation