Carbene Analogues of Group 15: Reduction of s-Hydrindacene-Based Chloropnictogenium Ions To Access an Antimony Hydride Monocation and a Trinuclear Bismuth Dication

High Resolution Image Download MS PowerPoint Slide We report the synthesis of three chloropnictogenium cations [M S FluindECl] + ( 2As, 2Sb and 2 Bi ), which unravel different reaction pathways toward Et 3 SiH, leading to the formation of the neutral arylarsenic(III) dihydride M S FluindAsH 2 ( 3 ), the cationic arylhydridostibenium(III) [M S FluindSbH] + ( 4 ) and the dicationic aryltribismuth(I) ion [M S FluindBi 3 ] 2+ ( 7 ). In light of its reactivity, 4 can also be regarded as a protonated stibinidene(I), as demonstrated by the reaction with trimethylindium and gallium as well as diphenyldichalcogenides, leading to the stibinidene supported dimethylelement cations [M S FluindSbEMe 2 ] + ( 5Ga, 5In ) and the chalcogenide cations [M S FluindSbChPh] + ( 6S, 6Se, 6Te ) featuring formal SbCh double bonds. The Bi 3 dication 7 reveals substantial 2-electron-3-center bonding character within the Bi–C–Bi interaction, a feature unprecedented in the chemistry of group 15 elements.