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) scaffold1, [1,2-(LSi)(2)C2B10H10; L=PhC((NBu)-Bu-t)(2)], reaction with adamantyl azide (AdN(3)) affords the terminal N-mu(2)-bridged zwitterionic carborane-1,2-bis(silylium) AdN(3)adduct2with an open-cage dianionic nido-C(2)B(10)cluster core. Remarkably, upon one-electron reduction of2with C8K 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 of3with the nido-C(2)B(10)cluster cage. On the other hand, one-electron oxidation of2with silver(I) yields the monocationic bis(silylene) N(I)complex4with the closo-C(2)B(10)cluster core. Moreover, the corresponding neutral N(I)radical complex5results from single-electron transfer from3to4.