Syntheses and Structures of Acetyl-Acetonato-Alumo-Diphenylsilanolates with Magnesium(II), Iron(II), Iron(III), Cobalt(II), and Nickel(II)

• Published in: Zeitschrift für anorganische und allgemeine Chemie (1950) Vol. 642; no. 3; pp. 204 - 210
• Main Authors: Veith, Michael, Smail-Bubel, Hakima, Nadig, Sandra, Huch, Volker
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 01.02.2016; WILEY‐VCH Verlag; Wiley Subscription Services, Inc
• Subjects: Acetylacetonate/silanolate; Aluminum; Iron-cobalt-nickel; Ligands; Magnesium; Metal aluminates; Nickel; X-ray diffraction
• ISSN: 0044-2313; 1521-3749
• DOI: 10.1002/zaac.201500758

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)2 by 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)2 cycle (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 MO4 coordination 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)3 was 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.