Matrix isolation infrared spectroscopic and theoretical study of the transition metal (Mn and Fe) dioxide–ethylene complexes

Formation and Characterization of the Photochemically Interconvertible Side-On and End-On Bonded Dioxygen−Iron Dioxide Complexes in Solid Argon

“…As shown in Figure , the O−O bond length was predicted to be 1.378 Å, which falls into the range of peroxide bond lengths; therefore, the (η 2 -O 2 )FeO 2 complex can be regarded as [(FeO 2 ) 2+ (O 2 2- )], a side-on bonded peroxo iron dioxide complex. The complex was predicted to have a smaller OFeO bond angle (121.4°) than those of the iron dioxide complexes with acetylene (130.6°) and ethylene (137.4°), which is consistent with the relatively larger isotopic frequency ratio of the antisymmtric OFeO stretching mode in the (η 2 -O 2 )FeO 2 complex. The mixed isotopic spectral features are complicated.…”

Metal Cluster Models for Heterogeneous Catalysis: A Matrix‐Isolation Perspective

“…The investigation of the reaction of matrix-isolated transition metal clusters is essentially restricted to the metal oxides, MO, and metal dioxides, MO 2 .R eactions with small inorganic molecules like H 2 O, [116][117][118] N 2 , [119][120][121] CO, [122] CO 2 , [123][124][125] and H 2 [126][127][128][129][130] as well as organic molecules like CH 4 , [131][132][133] CH 3 Cl, [134][135][136][137] CH 3 OH, [138] C 2 H 2 , [139][140][141][142] and C 2 H 4 [143] have been investigated. Reactions of monoxides MO with CH 4 have been reviewed by Wang and Zhou.…”

“…[142] For MnO 2 and FeO 2 ,t he reaction with ethylene has been probed, and the complexes MnO 2 (C 2 H 4 )a nd FeO 2 (C 2 H 4 )h ave been observed, which are stable upon UV/Vis irradiation. [143] For many of the reactions irradiation is necessary, indicating the importance of excited states.…”

A DFT Study on the Degradation of Chlorobenzene to p-chlorophenol via Stable Hydroxo Intermediate Promoted by Iron and Manganese Monoxides

“…Further DFT theoretical calculations on the spin inversion process of the reaction pathway were reported by Jin et al who considered two-state reactivity and spin-forbidden chemical reactions [17]. Besides the reactions of pure transition metal compounds with methane and acetonitrile, some small hydrocarbons such as C 2 H 2 , C 2 H 4 , and C 6 H 6 [18][19][20] and halohydrocarbons such as CH 3 Cl [21][22][23][24] have also been reported. However, the reactions of pure transition metal oxides with halogenated aromatic hydrocarbons have received very little attention.…”