No abstract

The Lewis acid assisted triflate/methyl, azide/methyl, and chlorine/methyl exchange reactions between silicon and antimony have been studied in the reaction of R(Me(3)Si)N-SbCl(2) (R = Ter) with AgOTf, AgN(3), KOtBu, GaCl(3), and Me(3)SiN(3)/GaCl(3), resulting in the formation of different methylantimony compounds. Furthermore, R(Me(3)Si)N-SbCl(2) (R = SiMe(3)) was reacted with GaCl(3) at low temperatures to yield a hitherto unreported amino(chloro)stibenium cation, the proposed intermediate in methyl exchange reactions. Tetrachloridogallate salts bearing different stibinostibonium cations such as [(Me(3)Sb)SbMe(2)](+) and [(Me(3)Sb)(2)SbMe](2+) along with the GaCl(3) adduct of SbMe(3) were isolated from such R(Me(3)Si)N-SbCl(2)/GaCl(3) mixtures (R = SiMe(3)) at ambient temperatures, depending on the reaction parameters.

Various new P-based ring systems were synthesised by transferring established reaction routes from NP chemistry to the analogous PP compounds. Due to the different electronic situations of phosphorus and nitrogen with respect to s and p character of the lone pair, different reactivity of the phosphorus compounds was observed, especially with regard to the specificity of the reactions and the stability of the products. Whereas Mes*NPCl (Mes*=2,4,6-tri-tert-butylphenyl) is stable in the solid state and in solution, the formal phosphorus congener Mes*PPCl is highly reactive and could not be observed. Instead, several formal dimers and trimers of Mes*PPCl could be isolated, which constitute an intriguing variety of three- and four-membered ring systems.