| Popis: |
The NH bond activation of ammonia, primary and secondary amines by tetramesityldisilene and -digermene was investigated. In each case, a disilyl- or digermylamine was formed as the only product of amine addition. The mechanism of the addition of ammonia to tetramesityldisilene was computed and revealed a three-step reaction pathway: formation of the anti-ammonia-disilene adduct, inversion at the β-silicon, and syn-transfer of the proton to give the syn-product, where each step follows a distinct stereochemical course. Examination of the reaction landscape also revealed several additional insights: (a) that, in the initial step, the formation of the anti-oriented zwitterionic intermediate is kinetically more preferable than formation of the syn-oriented zwitterionic intermediate, (b) that intermolecular transfer of a proton is not energetically feasible in non-polar solvents, and (c) that the bulk of the substituents can have a profound effect on the stereochemical course of the reaction. With this detailed understanding, nucleophilic additions to ditetrelenes can be exploited in the future. |
