Construction of larger molecular aluminophosphate cages from the cyclic four-ring building unit

New molecular aluminophosphates of different nuclearity are synthesized by a stepwise process and structurally characterized. The alkane elimination reaction of bis(trimethylsiloxy)phosphoric acid, OP(OH)(OSiMe3)2, with trialkylalanes, AlR3 (R = Me, Et, (i)Bu), provides the cyclic dimeric aluminophosphates, [(AlR2{μ2-O2P(OSiMe3)2})2] (R = Me (1), Et (2), (i)Bu (3)). Unsymmetrically substituted cyclic aluminophosphonate [(AlMe2{μ2-O2P(OSiMe3)((c)Hex)})2] (cis/trans-4) is prepared by dealkylsilylation reaction of (c)HexP(O)(OSiMe3)2 with AlMe3. Molecules 1-4 containing the [Al2(μ2-O2P)2] inorganic core are structural and spectroscopic models for the single four-ring (S4R) secondary building units (SBU) of zeolite frameworks. Compound 1 serves as a starting point in construction of larger molecular units by reactions with OP(OH)(OSiMe3)2 as a cage-extending reagent and with diketones, such as Hhfacac (1,1,1,5,5,5-hexafluoropentan-2,4-dione) and Hacac (pentan-2,4-dione), as capping reagents. Reaction of 1 with 4 equiv of Hhfacac leads to new cyclic aluminophosphate [(Al(hfacac)2{μ2-O2P(OSiMe3)2})2] (5), existing in two isomeric (D2 and C2h) forms. Reaction of 1 with 2 equiv of OP(OH)(OSiMe3)2 and 1 equiv of Hhfacac provides a molecular aluminophosphate [AlMe{Al(hfacac)}2{μ3-O3P(OSiMe3)}2{μ2-O2P(OSiMe3)2}2{OP(OSiMe3)3}] (6), while by adding first the Hhfacac and using 3 equiv of OP(OH)(OSiMe3)2 we isolate [Al{Al(hfacac)}2{μ3-O3P(OSiMe3)}2{μ2-O2P(OSiMe3)2}2H{OP(O)(OSiMe3)2}2] (7). These molecules contain units in their cores that imitate 4=1 SBU of zeolite frameworks. Reaction with the order of component mixing 1, Hhfacac, OP(OH)(OSiMe3)2 at a 1:2:2 molar ratio lead to formation of a larger cluster [(Al(AlMe){Al(hfacac)}{μ3-O3P(OSiMe3)}2{μ2-O2P(OSiMe3)2}3)2] (8) containing both S4R and 4=1 structural units. Similarly, Hacac (pentan-2,4-dione) provides an isostructural [(Al(AlMe){Al(acac)}{μ3-O3P(OSiMe3)}2{μ2-O2P(OSiMe3)2}3)2] (9). Both molecules display Al centers in three different coordination environments.