Multielectron\nReduction of Nitrosoarene via Aluminylene-Silylene\nCooperation

The\ncooperative effects of main-group elements pave the way for\nnovel chemical transformations. However, the potential of bimetallic\ncomplexes featuring the most abundant aluminum and silicon elements\nremains largely unexplored. In this study, we present the synthesis\nand characterization of bis(silylene)-stabilized aluminylene <b>2</b>. The cooperation between aluminylene and silylene allows\nfor the facile cleavage of the N–O bond in nitrosoarenes, producing\nan aluminum imide complex <b>4</b> and tetracyclic oxazasilaalanes <b>5</b> and <b>6</b>, and also promotes the dearomatization\nof 2-methylquinoline, yielding a silylalane <b>7</b>. In addition, <b>2</b> is an effective precatalyst for the reductive coupling of\nnitrosoarenes to azoxyarenes. These results outline an approach for\norchestrating aluminum and silicon cooperation to facilitate chemical\nbond activation.