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.