Cationic Complexes with Au→Ge Bonds - Synthesis and Carbophilic Reactivity

As part of our efforts to interface late 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. In the case of X = Cl, double chloride abstraction with AgSbF6 affords a putative dication that gradually abstracts fluoride from its counterion. This putative dication is also significantly more active as a catalyst than its monocationic analog in alkyne hydroamination reactions.

Automated summary

In this study, gold complexes with halogermanes as ligands were synthesized and investigated. Experimental and computational analyses revealed the presence of an Au -> Ge interaction in these complexes. Chloride abstraction reactions were also studied, and a putative dication was formed by double chloride abstraction with AgSbF6. This dication showed higher catalytic activity than its monocationic analog in alkyne hydroamination reactions.