Transformations of the polycyclic Alumosiloxane Al ₂ (OSiPh ₂ OSiPh ₂ O) ₃ into new Polycycles and Co(II) and In(III) derivatives of (Ph ₂ SiO) ₈ [Al(O)OH] ₄

In the presence of water and amines etherate bicyclic Al2(OSiPh2OSiPh2O)3 (II a) can be used to generate novel alumosiloxane polycycles like [O(Ph2SiOSiPh2)O−]2Al2O[O(Ph2SiOSiPh2)O] ⋅ 2 H2N+Et2 (1), [O(Ph2SiOSiPh2)O−]2Al2[O(Ph2Si)O]2 HN+Et3 (2), [O(Ph2SiOSiPh2)O−]2Al2[O(Ph2SiOSiPh2)O]2 (3 a, 3 b), which crystallizes in two different phases, HN+(CH2CH2)3N (4). As a common structural feature these compounds aluminum atoms are incorporated six-membered Al[O(SiPh2OSiPh2)O−] rings connected as spiro cyclic centers through oxygen and/or siloxane bridges [(OSiPh2)nO] (n=1, 2) form an assembly three fused at corners. The central ring is either eight- (1, or twelve-membered (3, 4). Alkyl ammonium cations balance charges hydrogen six membered rings. pentacyclic (Ph2SiO)8[Al(O)OH]4 (I) indirectly (addition water) directly chelating ligand versus Co(II)Cl In-CH3 fragments shown with isolated structurally characterized (HN+Et3)2{[(Ph2Si)2O3][Al4(OH)4O2](CoCl)2}2− (5 5 b) (Ph2SiO)8[AlO(OH)]2[AlO2]2(InCH3) O(CH2)4 (6).