Abstract
Two types of heterometallic (Fe(III),Na) silsesquioxanes—[Ph5Si5O10]2[Ph10Si10O21]Fe6(O2‒)2Na7(H3O+)(MeOH)2(MeCN)4.5.1.25(MeCN), I, and [Ph5Si5O10]2[Ph4Si4O8]2Fe6Na6(O2‒)3(MeCN)8.5(H2O)8.44, II—were obtained and characterized. X-ray studies established distinctive structures of both products, with pair of Fe(III)-O-based triangles surrounded by siloxanolate ligands, giving fascinating cage architectures. Complex II proved to be catalytically active in the formation of amides from alcohols and amines, and thus becoming a rare example of metallasilsesquioxanes performing homogeneous catalysis. Benzene, cyclohexane, and other alkanes, as well as alcohols, can be oxidized in acetonitrile solution to phenol—the corresponding alkyl hydroperoxides and ketones, respectively—by hydrogen peroxide in air in the presence of catalytic amounts of complex II and trifluoroacetic acid. Thus, the cyclohexane oxidation at 20 °C gave oxygenates in very high yield of alkanes (48% based on alkane). The kinetic behaviour of the system indicates that the mechanism includes the formation of hydroxyl radicals generated from hydrogen peroxide in its interaction with di-iron species. The latter are formed via monomerization of starting hexairon complex with further dimerization of the monomers.
Highlights
Heterometallic complexes and clusters are among the most popular objects of contemporary chemistry, due to several remarkable features
Fe,Na-phenylsilsesquioxane use of acetonitrile as a medium for synthesis/crystallization led to the isolation of unusual Fe,Na2
Catalytic Transformation of Alcohols and Amines into Amides performed using as low as 500 ppm of iron in the presence of tert-butylhydroperoxide (TBHP) as
Summary
Heterometallic complexes and clusters are among the most popular objects of contemporary chemistry, due to several remarkable features. The use of different metal ions is known as a key toCatalysts controlled of high-nuclearity complexes of picturesque molecular architecture
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