Metal-Organic Framework-Supported Mono Bipyridyl-Iron Hydroxyl Catalyst for Selective Benzene Hydroxylation into Phenol.

Direct hydroxylation of benzene to phenol is more appealing in the industry for the economic and environmentally friendly phenol synthesis than the conventional cumene process. We have developed a UiO-metal-organic framework (MOF)-supported mono bipyridyl-Iron(II) hydroxyl catalyst [bpy-UiO-Fe(OH)2] for the selective benzene hydroxylation into phenol using H2O2 as the oxidant. The heterogeneous bpy-UiO-Fe(OH)2 catalyst showed high activity and remarkable phenol selectivity of 99%, giving the phenol mass-specific activity up to 1261 mmolPhOHgFe-1 h-1 at 60 °C. Bpy-UiO-Fe(OH)2 is significantly more active and selective than its homogeneous counterpart, bipyridine-Fe(OH)2. This enhanced catalytic activity of bpy-UiO-Fe(OH)2 over its homogeneous control is attributed to the active site isolation of the bpy-Fe(OH)2 moiety by the solid MOF that prevents intermolecular decomposition. Moreover, the exceptional selectivity of bpy-UiO-Fe(OH)2 in benzene to phenol conversion is originated via shape-selective catalysis, where the confined reaction space within the porous UiO-MOF prevents the formation of larger overoxidized products such as hydroquinone or benzoquinone, leading to the formation of only smaller-sized phenol after monohydroxylation of benzene. Spectroscopic and controlled experiments and theoretical calculations elucidated the reaction pathway, in which the in situ generated •OH radical mediated by bpy-UiO-FeII(OH)2 is the key species for benzene hydroxylation. This work underscores the significance of MOF-supported earth-abundant metal catalysts for sustainable production of fine chemicals.

Selective monoborylation of methane by metal-organic framework confined mononuclear pyridylimine-iridium(I) hydride.

Chemoselective monoborylation of methane in high yield is a grand challenge. We have developed a metal-organic framework confined pyridylimine-iridium hydride catalyst, which is efficient in methane C-H borylation using bis(pinacolato)diboron to afford methyl boronic acid pinacol ester in 98% GC-yield at 130 °C with a TON of 196. Mechanistic investigation suggests the oxidative addition of methane to IrIII(Bpin)2(H) species to form IrV(Bpin)2(CH3)(H)2 as the turnover limiting step.

Selective Reduction of Nitro Compounds by Organosilanes Catalyzed by a Zirconium Metal-Organic Framework Supported Salicylaldimine-Cobalt(II) Complex.

Reducing nitro compounds to amines is a fundamental reaction in producing valuable chemicals in industry. Herein, the synthesis and characterization of a zirconium metal-organic framework-supported salicylaldimine-cobalt(II) chloride (salim-UiO-CoCl) and its application in catalytic reduction of nitro compounds are reported. Salim-UiO-Co displayed excellent catalytic activity in chemoselective reduction of aromatic and aliphatic nitro compounds to the corresponding amines in the presence of phenylsilane as a reducing agent under mild reaction conditions. Salim-UiO-Co catalyzed nitro reduction had a broad substrate scope with excellent tolerance to diverse functional groups, including easily reducible ones such as aldehyde, keto, nitrile, and alkene. Salim-UiO-Co MOF catalyst could be recycled and reused at least 14 times without noticeable losing activity and selectivity. Density functional theory (DFT) studies along with spectroscopic analysis were employed to get into a comprehensive investigation of the reaction mechanism. This work underscores the significance of MOF-supported single-site base-metal catalysts for the sustainable and cost-effective synthesis of chemical feedstocks and fine chemicals.

Selective Methane Oxidation to Acetic Acid Using Molecular Oxygen over a Mono-Copper Hydroxyl Catalyst.

Acetic acid is an industrially important chemical, produced mainly via carbonylation of methanol using precious metal-based homogeneous catalysts. As a low-cost feedstock, methane is commercially transformed to acetic acid via a multistep process involving energy-intensive methane steam reforming, methanol synthesis, and, subsequently, methanol carbonylation. Here, we report a direct single-step conversion of methane to acetic acid using molecular oxygen (O2) as the oxidant under mild conditions over a mono-copper hydroxyl site confined in a porous cerium metal-organic framework (MOF), Ce-UiO-Cu(OH). The Ce-UiO MOF-supported single-site copper hydroxyl catalyst gave exceptionally high acetic acid productivity of 335 mmolgcat-1 in 96% selectivity with a Cu TON up to 400 at 115 °C in water. Our spectroscopic and theoretical studies and controlled experiments reveal that the conversion of methane to acetic acid occurs via oxidative carbonylation, where methane is first activated at the copper hydroxyl site via σ-bond metathesis to afford Cu-methyl species, followed by carbonylation with in situ-generated carbon monoxide and subsequent hydrolysis by water. This work may guide the rational design of heterogeneous abundant metal catalysts for the activation and conversion of methane to acetic acid and other valuable chemicals under mild and environmentally friendly reaction conditions.