High Catalytic Activity of Heterometallic (Fe6Na7 and Fe6Na6) Cage Silsesquioxanes in Oxidations with Peroxides

Abstract

Two types of heterometallic (Fe(III),Na) silsesquioxanes

Ionic Complexes of Tetra‐ and Nonanuclear Cage Copper(II) Phenylsilsesquioxanes: Synthesis and High Activity in Oxidative Catalysis

“…Previously, we reported the ability of CLMSs to catalyze the oxidative formation of amides from alcohols . This reaction could be performed using Cu, Fe, or Zn, but the catalyst loading could not be decreased below 1 mol %.…”

“…This reaction could be performed using Cu, Fe, or Zn, but the catalyst loading could not be decreased below 1 mol %. With the use of CLMSs, this reaction was efficient with dramatically lower loadings (down to 100 ppm of Cu and 500 ppm of Fe). As 1 and 4 present really atypical structures, their catalytic activity was also evaluated in the transformation of benzylic alcohol into benzamide.…”

Recent Advances in Iron Catalyzed Oxidation Reactions of Organic Compounds

“…Farnetti investigated iron(II) 2,2’‐ bipyridine complexes in the oxidation of primary and secondary alcohols to provide the corresponding aldehydes and ketones in yields up to 100 % (Table , entry 8) . Shul'pin demonstrated that heterometallic (Fe III ,Na) silsesquioxanes are capable of oxidizing 2‐phenyl ethanol and cyclooctanol to the corresponding ketones in yields up to 92 % utilizing t BuOOH as the oxidant (entry 9) . Mahmudov, da Silva, and Pombeiro synthesized an iron formazan complex to be catalytically active in the solvent‐free, microwave‐assisted oxidation of phenyl ethanol (entry 10) .…”

Heptanuclear Cage CuII‐Silsesquioxanes: Synthesis, Structure and Catalytic Activity

“…Specific representatives of cage metallacomplexes, namely cagelike metallasilsesquioxanes (CLMSs), are being intensely studied as (pre)catalysts for numerous chemical processes of high relevance . Cage metallasilsesquioxanes were found to be active in alkene polymerization, epoxidation or epoxide ring opening, metathesis, hydroformylation, Ullmann–Goldberg condensation and amidation . Recently, significant attention was drawn to the potential of CLMS application in the homogeneous oxidation of C–H compounds with activity confirmed for Fe‐,, Cr‐, Ni‐, and Co‐based compounds.…”

“…Cage metallasilsesquioxanes were found to be active in alkene polymerization, epoxidation or epoxide ring opening, metathesis, hydroformylation, Ullmann–Goldberg condensation and amidation . Recently, significant attention was drawn to the potential of CLMS application in the homogeneous oxidation of C–H compounds with activity confirmed for Fe‐,, Cr‐, Ni‐, and Co‐based compounds. In turn, the best potential for this type of catalytic activity was found for Cu II ‐based cage silsesquioxanes.…”