Bis(silylene)‐Stabilized Monovalent Nitrogen Complexes
Shenglai Yao, Tibor Szilvási, Yun Xiong, Christian Lorent, Aleš Růžička, Matthias Drieß
Abstract
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 .