Abstract
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.