Oxyfunctionalization of Alkanes Based on a Tricobalt(II)-Substituted Dawson-Type Rhenium Carbonyl Derivative as Catalyst

Abstract

POM-supported metal carbonyl derivatives (PMCDs) represent a family of tremendous potential catalysts owing to their peculiar physical and chemical properties. Yet low-valence transition metal-substituted Dawson-type PMCD catalysts are uncommon. Hence, we synthesized a tricobalt-substituted PMCDs by conventional aqueous solution method, [Na(H 1), and characterized by single crystal X-ray diffraction crystallography, IR, and thermogravimetric analyses (TGA), etc. The obtained compound 1 was employed as a catalyst for the oxidation of diphenylmethane (DPM) to benzophenone, giving 96.8% yield in the presence of tert-butyl hydroperoxide (TBHP) and pyridine. The control experiments indicate that Co metal ion plays an important role in the catalytic reactions. As a side note, the electrospray ionization mass spectrometry (ESI-MS) and UV spectroscopy showed that 1 can retain its integrity in solution, and magnetic measurements indicated that 1 exhibited a weaker ferromagnetic interaction at low temperature.

A Copper-Containing Polyoxometalate-Based Metal–Organic Framework as an Efficient Catalyst for Selective Catalytic Oxidation of Alkylbenzenes

“…Moreover, the significant difference between HENU-7 and its raw materials for their catalytic transformation of DPM to BP distinctly indicated the great contribution of hierarchical structures of HENU-7 (Table , entries 5 and 8). , As far as we know, HENU-7 presents similar or better performance than known noble-metal-free POM-based catalysts in the literature (Table S4). In addition, one of the earlier reported catalysts has been synthesized and employed to catalyze this transformation (Table , entries 6 and 7; Table S4, entry 5) . And under the optimal conditions, the DPM conversion obtained over P 2 W 15 Co 3 is 51%, while the selectivity to BP is 98%.…”

“… a Reaction conditions: DPM (1 mmol), TBHP (3 mmol), catalyst (0.5 mol %), acetonitrile (0.5 mL), T = 75 °C, t = 24 h. b GC conversion for target product BP was based on naphthalene as internal standard. All of the products were identified by GC–MS spectra and GC spectra. c Selectivity for BP. d P 2 W 15 Co 3 = [Na­(H 2 O) 5 ]­(NH 4 ) 7 ­[P 2 W 15 ­O 56 Co 3 ­(H 2 O) 3 (OH) 3 Re­(CO) 3 ]·13H 2 O. Pyridine as the additive (0.3 mmol) …”

“… d P 2 W 15 Co 3 = [Na­(H 2 O) 5 ]­(NH 4 ) 7 ­[P 2 W 15 ­O 56 Co 3 ­(H 2 O) 3 (OH) 3 Re­(CO) 3 ]·13H 2 O. Pyridine as the additive (0.3 mmol) …”

“…Polyoxometalates (POMs), as a class of nanosized discrete anionic metal-oxide clusters, have drawn enormous attention and are applied widely in many fields (e.g., magnetism, medicine, electrochemistry, and especially in catalysis) because of their unique physicochemical properties. − In recent years, many researchers have demonstrated POM-based catalysts did have praiseworthy catalytic performance for selective oxidation of DPM to BP. − However, POMs suffer from some intrinsic drawbacks, including low specific surface area, high water solubility, and difficult separation (reuse), which shackle the further industrial applications of POMs. ,,− Therefore, a promising solution is to select a proper carrier and load the POMs . Simultaneously, metal–organic frameworks (MOFs), which have tunable nanospaces providing satisfactory accommodation for multitudinous guest species, have been regarded as a new class of porous materials. − Thanks to their inherent tunability, MOFs have cumulative application in gas storage, magnetism, fluorescence, and catalysis.…”

Dimensional Reduction ofEu‐Based Metal‐OrganicFramework as Catalysts for Oxidation Catalysis of C(sp3)–H Bond

“…It is speculated to be caused by the differences of coordiantion number of the active sites (Eu III ions). According to previous literatures [ 52‐56 ] and description above, a possible mechanism is supposed as Figure S16. In the reaction, Eu‐based MOF played as a Lewis acid, and TBHP played as a Lewis base.…”