Bis(acetylacetonate)alumo-oxo-tetraphenyldisiloxane-metal(II) dihydrates [(acac)2Al(O–SiPh2–O–SiPh2–O)]2M(H2O)2(M = Mg, Fe, Co, Ni) were obtained from the corresponding acetyl-acetonate-dihydrates (acac)2M(H2O)2by reaction with the alumosiloxane [O–Ph2Si–O–SiPh2–O]4Al4(OH)4. These new compounds display two acac ligands at the aluminum atoms as well as disilatrioxy chains linking the two aluminum atoms forming a (Al–O–Si–O–Si–O)2cycle (X-ray structure analyses). Within this cycle the divalent metal ions M2+, to which two water molecules in trans positions are linked, are installed in almost planar MO4coordination spheres. Using water free (acac)2Ni a different product forms: both reactants combine in a 2:1 ratio to yield [O–Ph2Si–O–SiPh2–O]4Al4(OH)2O(OH2)Ni2(acac)4. Here, three of the acac ligands were transposed to the aluminum atoms. The nickel atoms are in a distorted octahedral coordination mode from oxygen atoms of the ligands. When iron(III)tris(acetylacetonate) reacts with the alumosiloxane [O–Ph2Si–O–SiPh2–O]3Al2O(OH)Fe2(acac)3was isolated, in which the two iron atoms still display one of the acac ligands. One of the aluminum atoms is in a tetrahedral oxygen environment, whereas the other is in the center of a trigonal bi-pyramid formed of oxygen atoms either of the siloxane or of acac. The iron atoms have five- or sixfold coordination from oxygen atoms of siloxane, acac, hydroxide or oxide.