Alkoxo‐Verbindungen des dreiwertigen Eisen: Synthese und Charakterisierung von [Fe₂(OtBu)₆], [Fe₂Cl₂(OtBu)₄], [Fe₂Cl₄(OtBu)₂] und [N(nBu)₄]₂[Fe₆OCl₆(OMe)₁₂]

Abstract

Inhaltsübersicht. Durch Reaktion von Eisen(III)-chlorid in Diethylether mit Natrium-tert-butylat konnte das homoleptische dimere tert-Butoxid [Fe 2 (OtBu) 6 ] (1) hergestellt werden. Die Chloro-Derivate [Fe 2 Cl 2 (OtBu) 4 ] (2) und [Fe 2 Cl 4 (OtBu) 2 ] (3) wurden durch Liganden-Austausch zwischen 1 und Eisen(III)-chlorid synthetisiert. In 1, 2 und 3 liegen jeweils zwei kantenverknüpfte Tetraeder mit zwei tert-Butoxo-Gruppen als Brückenliganden vor. Eine entscheidende Rolle für die Synthese von 1, 2 und 3 spielt das verwendete Abstract. The reaction of iron(III)chloride in diethylether with sodium tert-butylat yielded the homoleptic dimeric tert-butoxide Fe 2 (OtBu) 6 (1). The chloro-derivatives [Fe 2 Cl 2 (OtBu) 4 ] (2), and [Fe 2 Cl 4 (OtBu) 2 ] (3) could be synthesized by ligand exchange between 1 and iron(III)chloride. Each of the molecules 1, 2, and 3 consists of two edge-sharing tetrahedrons, with two tert-butoxogroups as µ 2 -bridging ligands. For the synthesis of the alkoxides 1, 2, and 3 diethylether plays an important role. In the first step the dietherate of iron(III)chloride FeCl 3 (OEt 2 ) 2 (4) is formed. The reaction of iron(III)chloride with tetrabutylammonium methoxide in methanol results in the formation of a tetrabutylammonium methoxo-chloro-oxo-hexairon cluster [N(nBu) 4 ] 2 [Fe 6 OCl 6 (OMe) 12 ] (5).Crystal structure data: 1, triclinic, P1, a ϭ 9.882(2) Å , b ϭ 10.523 (2) Å , c ϭ 15.972(3) Å , α ϭ 73.986(4)°, β ϭ 88.713(4)°, γ ϭ Einleitung Metallalkoxide [1] und deren Derivate zeigen eine große Vielfalt in ihren chemischen Eigenschaften und Verwendungszwecken. Sie werden u. a. als Katalysatoren bei einer Reihe von organischen Reaktionen sowie als Reaktanden für Sol-Gel-oder CVD-Verfahren zur Erzeugung von hochreinen Metalloxiden eingesetzt [2, 3, 4]. So können Eisen-Alkoxo-Verbindungen, um ein Beispiel zu nennen, die Polymerisation

Ferromagnetic Nanostructures by Atomic Layer Deposition: From Thin Films Towards Core-Shell Nanotubes

“…For atomic layer deposition of Fe 2 O 3 , water and the homoleptic dinuclear iron(III) tertbutoxide complex, Fe 2 (O t Bu) 6 were also used [22][23][24] . Fe 2 (O t Bu) 6 was synthesized according to published procedures and handled in inert atmosphere.…”

A Series of Homo‐ and Heteroleptic Iron(III) Alkoxides as Precursors for Fe2O3

“…Due to the steric demand of the tert ‐butyl group, iron tert ‐butoxide could be isolated as [Fe(O t Bu) 3 ] 2 . Spandl et al used this dimer as starting material in a ligand exchange reaction with iron(III) chloride and were able to isolate the heteroleptic compounds [Fe(O t Bu)Cl 2 ] 2 and [Fe(O t Bu) 2 Cl] 2 with dimeric structures as well …”

[Fe19] “Super‐Lindqvist” Aggregate and Large 3D Interpenetrating Coordination Polymer from Solvothermal Reactions of [Fe2(OtBu)6] with Ethanol

“…[24][25][26] Interestingly,o nly few molecular metal-oxygen compounds with more than three m 6 -oxo groups have been reported. [27][28][29][30] In the present work, we aimed for the synthesis of polynuclear iron-oxygen species comprising more than two m 6 -oxo groups.F or the formation of highly aggregated and spherical metal-oxygen complexes,small organic moieties of simple alkoxo groups (methoxo or ethoxo) appeared to be the most suitable.Each just allows the saturation of asmall area, minimizing the ratio between surface and volume of the aggregate.T hus,w ep ostulated that this should lead to complexes with spherical-like shapes.Thes olvothermal reaction of [Fe 2 (OtBu) 6 ] [21,31] with ethanol and tetrabutylammonium ethoxide at 115 8 8Cresulted in the formation of 1 (see the Supporting Information). Single-crystal X-ray diffraction analysis revealed its structure to be [HFe 19 Table S1).…”

“…[15] Molecular metal-oxygen compounds can be considered as 3D extracts of metal oxides.O ne indication for the achieved three-dimensionality of large aggregates is the number of incorporated m 6 -oxo groups.T here are several examples of polyoxoferrates with one m 6 -oxo group. [17][18][19][20][21][22] They possess ah ighly symmetrical hexanuclear Lindqvist [Fe 6 O 19 ]c ore. [23] Thef usion of two such [Fe 6 O 19 ]o ctahedra by one common edge results in the well-known decametalate structure comprising a[ Fe 10 O 28 ]f ramework. [24][25][26] Interestingly,o nly few molecular metal-oxygen compounds with more than three m 6 -oxo groups have been reported.…”