Alkoholyse von [Fe₂(O^tBu)₆] als einfacher Weg zu neuen Eisen(III)‐Alkoxo‐Verbindungen: Synthesen und Kristallstrukturen von [Fe₂(O^tAmyl)₆], [Fe₅OCl(OⁱPr)₁₂], [Fe₅O(OⁱPr)₁₃], [Fe₅O(OⁱBu)₁₃], [Fe₅O(OCH₂CF₃)₁₃], [Fe₅O(OⁿPr)₁₃] und

Abstract

Alcoholysis of [Fe2(OtBu)6] as a Simple Route to New Iron(III)‐Alkoxo Compounds: Synthesis and Crystal Structures of [Fe2(OtAmyl)6], [Fe5OCl(OiPr)12], [Fe5O(OiPr)13], [Fe5O(OiBu)13], [Fe5O(OCH2CF3)13], [Fe5O(OnPr)13], and [Fe9O3(OnPr)21] · nPrOH New alkoxo‐iron compounds can be synthesized easily by alcoholysis of [Fe2(OtBu)6] (1). Due to different bulkyness of the alcohols used, three different structure types are formed: [Fe2(OR)6], [Fe5O(OR)13] and [Fe9O3(OR)21] · ROH. We report synthesis and crystal structures of the compounds [Fe5OCl(OiPr)12] (2), [Fe2(OtAmyl)6] (3), [Fe5O(OiPr)13] (4), [Fe5O(OiBu)13] (5), [Fe5O(OCH2CF3)13] (6), [Fe9O3(OnPr)21] · nPrOH (7) and [Fe5O(OnPr)13] (8). Crystallographic Data: 2, tetragonal, P 4/n, a = 16.070(5) Å, c = 9.831(5) Å, V = 2539(2) Å3, Z = 2, dc = 1.360 gcm−3, R1 = 0.0636; 3, monoclinic, P 21/c, a = 10.591(5) Å, b = 10.654(4) Å, c = 16.740(7) Å, β = 104.87(2)°, V = 1826(2) Å3, Z = 2, dc = 1.154 gcm−3, R1 = 0.0756; 4, triclinic, $P{\bar 1}$, a = 20.640(3) Å, b = 21.383(3) Å, c = 21.537(3) Å, α = 82.37(1)°, β = 73.15(1)°, γ = 61.75(1)°, V = 8013(2) Å3, Z = 6, dc = 1.322 gcm−3, R1 = 0.0412; 5, tetragonal, P 4cc, a = 13.612(5) Å, c = 36.853(5) Å, V = 6828(4) Å3, Z = 4, dc = 1.079 gcm−3, R1 = 0.0609; 6, triclinic, $P{\bar 1}$, a = 12.039(2) Å, b = 12.673(3) Å, c = 19.600(4) Å, α = 93.60(1)°, β = 97.02(1)°, γ = 117.83(1)°, V = 2600(2) Å3, Z = 2, dc = 2.022 gcm−3, R1 = 0.0585; 7, triclinic, $P{\bar 1}$, a = 12.989(3) Å, b = 16.750(4) Å, c = 21.644(5) Å, α = 84.69(1)°, β = 86.20(1)°, γ = 77.68(1)°, V = 4576(2) Å3, Z = 2, dc = 1.344 gcm−3, R1 = 0.0778; 8, triclinic, $P{\bar 1}$, a = 12.597(5) Å, b = 12.764(5) Å, c = 16.727(7) Å, α = 91.94(1)°, β = 95.61(1)°, γ = 93.24(2)°, V = 2670(2) Å3, Z = 2, dc = 1.323 gcm−3, R1 = 0.0594.

Oxoethoxide Chlorides – Representatives of Oligonuclear Alkoxide Complexes of Gallium: Penta‐ and Dodecanuclear Molecules

“…Four shorter bridges are placed between the apical hexacoordinate metal atom and the equatorial metal atoms (designated as (5)(6) in Table 1), and the other four longer bridges bind the trigonal bipyramidal coordinated Ga atoms together in the equatorial plane (designated as in Table 1), see Figure 1. The bonding parameters for 1 are practically identical to those of its structural analogsderivatives of aluminium and iron(III), [15][16][17][18][19] see Table 1. The only (minor) difference between the compounds presented in Table 1 12 Cl.…”

“…The only (minor) difference between the compounds presented in Table 1 12 Cl. [19] Ga 5 O(OEt) 8 tween the axial and the equatorial metal atoms, are they cap the faces of the pyramid instead of the edges. In the other molecules presented in Table 1, the sums of the equatorial angles at the µ 5 -O groups are ca.…”

Unusual Reactivity of Silicon Grease Towards Metal Alkoxides: Serendipity for Structural Chemistry

“…The metal oxo‐alkoxide [Sn 2 In 2 O 2 {Me 2 Si(O i Pr)O}(O i Pr) 5 ] 2 crystallized in a monoclinic crystal system (space group P 2 1 / c, Table 1) with two molecules per cell unit (Figure 6). The formation of an oxo species could be explained by ether elimination, which was observed for other metal alkoxides such as [In 5 ( μ 5 ‐O)( μ 3 ‐O i Pr) 4 ( μ 2 ‐O i Pr) 4 (O i Pr) 5 ] [65,66] …”

“…The formation of an oxo species could be explained by ether elimination, which was observed for other metal alkoxides such as [In 5 (μ 5 -O)(μ 3 -OiPr) 4 (μ 2 -OiPr) 4 (OiPr) 5 ]. [65,66] The In2 metal center with one coordinated {OSiMe 2 (OiPr)} À unit is connected with two other indium and tin atoms through To illuminate the coordination of {Me 2 SiO} units, provided by grease in synthesis reaction with metal alkoxides, systematic activation of dimethylsiloxane and silicon grease with different reaction conditions have been performed. The hydrolysis of dimethylsiloxane was tried to initialize by the addition of alcohol in acidic as well as alkaline conditions in CAN solutions.…”

Molecular Level Synthesis of InFeO3 and InFeO3/Fe2O3 Nanocomposites

“…The selective conversion of a large number of metal alkoxides to ternary ceramics and composites has been demonstrated to verify the role precursor chemistry plays in the synthesis of phase pure material. ,,− ,,− ,− The formation of nanoscaled composites from molecular sources allows to tailor the material properties not possible by conventional synthesis methods, which generally lead to elemental segregation and phase separation. The sol–gel processing and gas phase depositions of monometallic metal alkoxides as single-source precursors are comprehensively studied; however, mixed-metal compositions are relatively less investigated. ,− ,,,,− Despite the potential advantages of chemical processing, the major constraint in the application of heterometallic alkoxides is related to their limited synthetic access and dearth of structural data on metal alkoxide frameworks.…”