Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 59, Issue 4, Pages 1445-1449Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201909551
Keywords
catalysis; C-O bond cleavage; hydrogenolysis; nickel; reaction mechanisms
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Funding
- U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences (BES), Division of Chemical Sciences, Geosciences and Biosciences (Transdisciplinary Approaches to Realize Novel Catalytic Pathways to Energy Carriers) [FWP 47319]
- DOE's Office of Biological and Environmental Research
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The hydrogenolysis of the aromatic C-O bond in aryl ethers catalyzed by Ni was studied in decalin and water. Observations of a significant kinetic isotope effect (k(H)/k(D)=5.7) for the reactions of diphenyl ether under H-2 and D-2 atmosphere and a positive dependence of the rate on H-2 chemical potential in decalin indicate that addition of H to the aromatic ring is involved in the rate-limiting step. All kinetic evidence points to the fact that H addition occurs concerted with C-O bond scission. DFT calculations also suggest a route consistent with these observations involving hydrogen atom addition to the ipso position of the phenyl ring concerted with C-O scission. Hydrogenolysis initiated by H addition in water is more selective (ca. 75 %) than reactions in decalin (ca. 30 %).
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