Some aspects of chemistry of the N→Si chelated aryloxydihydrosilanes R(ArO)SiH2(RPh, ArO) and of the 2,2-diaryloxytrisilane (Me3Si)2Si(OAr)2{ArO2,4,6-[(CH3)2NCH2]3C6H2O}

Reactions of the pentacoordinate aryloxydihydrosilane Ph(ArO)SiH2 (1) with hydroxyl groups, carbonyl derivatives and PCl5 resulted in formation of new alcoxylated, phenoxylated and halogenated hydrosilanes Ph(ArO)(H)X (X=Cl, OR, OAr, OC(O)R) respectively. Treatment of the hexacoordinated (4+2) diaryloxydihydrosilane (ArO)2SiH2 (2) with N-chloro- or N-bromosuccinimide, trimethylsilyltriflate or iodine yielded the novel stable silicenium ion [(ArO)2(H)Si]+X−. Reactions of 2 with sulfur S8 and the transition metal complex Fe(CO)5 have resulted in the isolation of the new complexes (ArO)2SiE [E=S, Fe(CO)4]. Decomposition modes of the tetracoordinate 2,2-diaryloxytrisilane (Me3Si)2Si(OAr)2 (3) on thermolysis and photolysis have also been studied; two pathways involving formation of the two silylenes (ArO)(Me3Si): and (ArO)2Si: have been identified by trapping experiments.