A Hexanuclear Iron(III) Carboxylate with an [Fe₆(μ₃‐O)₃(μ₂‐OH)]¹¹⁺ Core as an Efficient Catalyst for Cycloalkane Oxidation

Abstract

Catalytic alkane functionalization continues to attract the attention of researchers.[1] Starting with the discovery of the platinum(ii)-catalyzed activation of unfunctionalized alkanes, [2] a variety of activating systems involving organometallic species [3, 4] have been developed. In addition numerous catalytic systems based on high-valent metal complexes, such as metal-oxo complexes, [1i, 5]

Cage‐like Fe,Na‐Germsesquioxanes: Structure, Magnetism, and Catalytic Activity

“…This yield is one of the highest values obtained so far in metal‐catalyzed oxidations of cyclohexane with H 2 O 2 since usually yields are not higher than 5–30 %. For example, cyclohexane oxidation with H 2 O 2 catalyzed by a hexanuclear iron(III) carboxylate gave maximum yield of oxygenates of 29 %.…”

Molecular iron complexes as catalysts for selective C–H bond oxygenation reactions

“…127 Equal amounts of alcohol and ketone are formed in the catalytic oxidation of cyclohexane with H2O2 using a hexanuclear iron(III) complex carrying nitrobenzoate ligands (53, Figure 10). 128 A mixed-valent trinuclear iron complex bearing tetramethylreductic acid ligands (H2TMRA, 54) was used for the oxidation of cyclohexane with O2 as the terminal oxidant (Table 1). 129 Under addition of excess H2TMRA the reaction yields 14% products with an A/K ratio of 7.…”

Fe-Catalyzed Oxidation Reactions of Olefins, Alkanes, and Alcohols: Involvement of Oxo- and Peroxo Complexes

“…In 2008, we introduced an FeCl 3 Á6H 2 O ligand-free catalyst system for the a-oxidation of b-ketoesters (Scheme 12) [85]. By using cyclic b-ketoesters as starting material 75 core is the most active catalyst [86]. In the oxidation of cyclohexane with only 0.3 mol% of the hexanuclear iron complex, total yields up to 30% of the corresponding alcohol and ketone were achieved with 50% H 2 O 2 (5.5-8 equiv.)…”