Multielectron Reduction of Nitrosoarene via Aluminylene-Silylene Cooperation

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 <b>2</b>. The cooperation between aluminylene and silylene allows for the facile cleavage of the N-O bond in nitrosoarenes, producing an aluminum imide complex <b>4</b> and tetracyclic oxazasilaalanes <b>5</b> and <b>6</b>, and also promotes the dearomatization of 2-methylquinoline, yielding a silylalane <b>7</b>. In addition, <b>2</b> 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.