Bis(silylene)‐Stabilized Monovalent Nitrogen Complexes

The first series of bis(silylene)‐stabilized nitrogen(I) compounds is described. Starting from the 1,2‐bis(N‐heterocyclic silylenyl) 1,2‐dicarba‐closo‐dedocaborane(12) scaffold 1 , [1,2‐(LSi) 2 C 2 B 10 H 10 ; L=PhC(N t Bu) 2 ], reaction with adamantyl azide (AdN 3 ) affords the terminal N‐μ 2 ‐bridged zwitterionic carborane‐1,2‐bis(silylium) AdN 3 adduct 2 with an open‐cage dianionic nido‐C 2 B 10 cluster core. Remarkably, upon one‐electron reduction of 2 with C 8 K and liberation of N 2 and adamantane, the two silylene subunits are regenerated to furnish the isolable bis(silylene)‐stabilized N I complex as an anion of 3 with the nido‐C 2 B 10 cluster cage. On the other hand, one‐electron oxidation of 2 with silver(I) yields the monocationic bis(silylene) N I complex 4 with the closo‐C 2 B 10 cluster core. Moreover, the corresponding neutral N I radical complex 5 results from single‐electron transfer from 3 to 4 .