Transformations of the polycyclic Alumosiloxane Al₂(OSiPh₂OSiPh₂O)₃ into new Polycycles and Co(II) and In(III) derivatives of (Ph₂SiO)₈[Al(O)OH]₄

Abstract

In the presence of water and amines the etherate of bicyclic Al 2 (OSiPh 2 OSiPh 2 O) 3 (II a) can be used to generate novel alumosiloxane polycycles like [O(Ph 2 SiOSiPh 2 ) O À ] 2 Al 2 O[O(Ph 2 SiOSiPh 2 )O] • 2 H 2 N + Et 2 (1), [O(Ph 2 SiOSiPh 2 ) O À ] 2 Al 2 [O(Ph 2 Si)O] 2 • 2 HN + Et 3 (2), [O(Ph 2 SiOSiPh 2 ) O À ] 2 Al 2 [O(Ph 2 SiOSiPh 2 )O] 2 • 2 HN + Et 3 (3 a, 3 b), which crystallizes in two different phases, and [O(Ph 2 SiOSiPh 2 ) O À ] 2 Al 2 [O(Ph 2 SiOSiPh 2 )O] 2 • 2 HN + (CH 2 CH 2 ) 3 N (4). As a common structural feature of these compounds two aluminum atoms which are incorporated in six-membered Al[O(SiPh 2 OSiPh 2 )O À ] rings are connected as spiro cyclic centers through oxygen and/ or siloxane bridges [(OSiPh 2 ) n O] (n = 1, 2) to form an assembly of three fused rings at the aluminum corners. The central ring is either eight-(1, 2) or twelve-membered (3, 4). Alkyl ammonium cations balance the charges and form hydrogen bridges to oxygen atoms of the six membered rings. The pentacyclic (Ph 2 SiO) 8 [Al(O)OH] 4 (I) can be used indirectly (addition of water) and directly as chelating ligand versus Co(II)Cl and In-CH 3 fragments as shown with the isolated and structurally characterized compounds (HN + Et 3 ) 2 {[(Ph 2 Si) 2 O 3 ][Al 4 (OH) 4 O 2 ](CoCl) 2 } 2À (5 a, 5 b) and (Ph 2 SiO) 8 [AlO(OH)] 2 [AlO 2 ] 2 (InCH 3 ) • 2 O(CH 2 ) 4 (6).