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(Nt 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 NI 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) NI complex 4 with the closo-C2 B10 cluster core. Moreover, the corresponding neutral NI radical complex 5 results from single-electron transfer from 3 to 4.

Department of Chemical and Biological Engineering University of Wisconsin Madison 1415 Engineering Drive Madison WI 53706 USA

Department of Chemistry Metalorganics and Inorganic Materials Technische Universität Berlin Strasse des 17 Juni 135 Sekr C2 10623 Berlin Germany

Department of Chemistry Physical and Biophysical Chemistry Technische Universität Berlin Strasse des 17 Juni 135 Sekr PC14 10623 Berlin Germany

Department of General and Inorganic Chemistry Faculty of Chemical Technology University of Pardubice Studentska 573 532 10 Pardubice Czech Republic

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Access to cationic polyhedral carboranes via dynamic cage surgery with N-heterocyclic carbenes

Changing the Reactivity of Zero- and Mono-Valent Germanium with a Redox Non-Innocent Bis(silylenyl)carborane Ligand