Protonation of Hydrido‐Tetrylenes: H<sub>2</sub>Elimination vs. Tetrylium Cation Formation
Philip M. Keil, Terrance J. Hadlington
Abstract
Abstract We describe the reactions of amido‐E II hydride complexes, PhiP DippEH ( PhiP Dipp={[Ph 2 PCH 2 Si i Pr 2 ](Dipp)N} − ; Dipp=2,6‐ i Pr 2 C 6 H 3 ; E=Ge ( 5 ), Sn ( 6 )), towards the oxonium complex [(Et 2 O) 2 H][BAr F 4 ] (Ar F =3,5‐CF 3 ‐C 6 H 3 ). For 5 , formation of the dihydro‐tetrylium complex ( i. e . [ PhiP DippGeH 2 ][BAr F 4 ], ( 7 )) is favoured, in contrast to the same reaction for 6 which selectively leads to H 2 elimination, furnishing the novel tetryliumylidene [ PhiP DippSn][BAr F 4 ] ( 4 ). The related cationic Ge II complex ( i. e . [ PhiP DippGe][BAr F 4 ] ( 3 )) could be accessed via the often utilised chloride abstraction route with Na[BAr F 4 ]. The high Lewis acidity of this species has been demonstrated through the reaction of 3 towards the nitrogen bases, NH 3 and 4‐dimethylaminopyridine. In the latter case, a classic donor‐acceptor complex is formed. Conversely, for NH 3 , the [DippN] fragment of the ligand is intriguingly displaced by [HN], presumably through double proton‐transfer in loss of DippNH 2 .