Bis(silylene)‐Stabilized Monovalent Nitrogen Complexes. (28th September 2020)

• Record Type: Journal Article
• Authors: Yao, Shenglai; Szilvási, Tibor; Xiong, Yun; Lorent, Christian; Ruzicka, Ales; Driess, Matthias
• Is Part Of: Angewandte Chemie. Volume 132:Number 49(2020)
• Page Start: 22227
• Page End: 22231
• Publication Date: 2020-09-28
• Subjects: azides -- carboranes -- nitrogen complexes -- redox non-innocent ligands -- silylenes; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.202011598
• Languages: English
• ISSNs: 0044-8249

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 C2 B10 H10 ; L=PhC(N t Bu)2 ], reaction with adamantyl azide (AdN3 ) affords the terminal N‐μ2 ‐bridged zwitterionic carborane‐1, 2‐bis(silylium) AdN3 adduct 2 with an open‐cage dianionic nido‐C2 B10 cluster core. Remarkably, upon one‐electron reduction of 2 with C8 K and liberation of N2 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‐C2 B10 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‐C2 B10 cluster core. Moreover, the corresponding neutral N I radical complex 5 results from single‐electron transfer from 3 to 4 . Abstract : Starting from the unusual end‐on neutral bis(silylium) nido ‐carborane N3 Ad adduct 1, one‐electron reduction with KC8 in the presence of 18‐c‐6 leads to the K(18‐C‐6) salt 2 with the first anionic N I complex and a bis(silylenyl) nido ‐carborane ligand scaffold. One‐electron oxidation of 1 with silver(I) affords the cationic N I complex 3, which features a bis(silylenyl) closo ‐carborane ligand. Ad=adamantyl; 18‐C‐6=18‐crown‐6.