Selective Monoborylation of Methane by a Mono Bipyridyl-Nickel(II) Hydride Catalyst.

We report the development of an earth-abundant metal catalyst for methane C-H borylation. The post-synthetic metalation of bipyridine-functionalized zirconium metal-organic framework (MOF) with NiBr, followed by treatment with NaEtBH affords MOF-supported monomeric bipyridyl-nickel(II) dihydride species via active site isolation. The heterogeneous and recyclable nickel catalyst selectively borylates methane at 200 °C using pinacolborane (HBpin) to afford CHBpin in 61 % yield with a turnover number (TON) up to 1388.

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)] for the selective benzene hydroxylation into phenol using HO as the oxidant. The heterogeneous bpy-UiO-Fe(OH) catalyst showed high activity and remarkable phenol selectivity of 99%, giving the phenol mass-specific activity up to 1261 mmolg h at 60 °C.

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 Ir(Bpin)(H) species to form Ir(Bpin)(CH)(H) as the turnover limiting step.

A supported pyridylimine-cobalt catalyst for -formylation of amines using CO.

-Formylation of amines with CO as a cheap and non-toxic C1-feedstock and hydrosilane reducing agent is a practical and environment friendly method to synthesize formamides. This study describes an efficient and chemoselective mono--formylation of amines using CO and phenylsilane under mild conditions using a porous metal-organic framework (MOF)-supported single-site cobalt catalyst (pyrim-UiO-Co). The pyrim-UiO-Co MOF has a UiO-topology, and its organic linkers bear a pyridylimine ligated Co catalytic moiety.