南开大学莫贞波团队报道了亚硝基芳烃在铝-硅协同作用下的多电子还原。相关研究成果于2024年10月17日发表在《美国化学会杂志》。

主族元素的协同效应为新的化学转化铺平了道路。然而，以最丰富的铝和硅元素为特征的双金属复合物的潜力，在很大程度上仍未得到探索。

该文中，研究人员介绍了双（亚硅基）稳定的亚铝基2的合成和表征。亚铝和亚硅烯之间的合作可以很容易地裂解硝基芳烯中的N-O键，产生酰亚胺铝络合物4和四环氧杂硅丙氨酸5和6，还可以促进2-甲基喹啉的脱芳基化，产生甲硅烷7。

此外，2是亚硝芳烃还原偶联为偶氮氧芳烃的有效预催化剂。这些结果概述了一种协调铝和硅合作以促进化学键活化的方法。

附：英文原文

Title: Multielectron Reduction of Nitrosoarene via Aluminylene-Silylene Cooperation

Author: Xi Chen, Dezhi Yang, Fanshu Cao, Zhenbo Mo

Issue&Volume: October 17, 2024

Abstract: The cooperative effects of main-group elements pave the way for novel chemical transformations. However, the potential of bimetallic complexes featuring the most abundant aluminum and silicon elements remains largely unexplored. In this study, we present the synthesis and characterization of bis(silylene)-stabilized aluminylene 2. The cooperation between aluminylene and silylene allows for the facile cleavage of the N–O bond in nitrosoarenes, producing an aluminum imide complex 4 and tetracyclic oxazasilaalanes 5 and 6, and also promotes the dearomatization of 2-methylquinoline, yielding a silylalane 7. In addition, 2 is an effective precatalyst for the reductive coupling of nitrosoarenes to azoxyarenes. These results outline an approach for orchestrating aluminum and silicon cooperation to facilitate chemical bond activation.

DOI: 10.1021/jacs.4c10323

Source: https://pubs.acs.org/doi/abs/10.1021/jacs.4c10323