Importance of Methane Chemical Potential for Its Conversion to Methanol on Cu‐Exchanged Mordenite
Not Available
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Engineering topics
Camaioni, Donald M.
Publications and source records attributed to Camaioni, Donald M..
Aqueous phase catalytic and electrocatalytic hydrogenation of phenol and benzaldehyde over platinum group metals
Abstract not provided
Singh, Nirala↗
The Critical Role of Reductive Steps in the Nickel-Catalyzed Hydrogenolysis and Hydrolysis of Aryl Ether C-O Bonds
Hydrogenolysis of the aromatic C-O bond in aryl ethers is catalyzed by Ni in decalin or water at 150 °C. Observations of a significant kinetic isotope effect (kH/kD = 5.7) for the reactions of diphenyl ether under H2 and D2 and a positive dependence of the rate on H2 chemical potential in decalin indicate that addition of H to the aromatic ring is the rate-limiting step rather than C-O scission. Hydrogen addition occurs on the metal before C-O bond scission. DFT calculations indicate that hydrogen atom addition to the ortho position followed by C-O scission is energetically more feasible than C-O scission followed by H addition to either phenoxyl or phenyl moieties. Hydrogenolysis initiated via H addition in water is more selective (~75 %) compared to reactions in decalin (~30 %). The high selectivity for hydrogenolysis is attributed to stabilization of polar transition state by water as a polar solvent.
Wang, Meng↗