Work

Nickel-Mediated Hydrogenolysis of C–O Bonds of Aryl Ethers: What Is the Source of the Hydrogen?

Year: 2012

Type: article

Abstract: Mechanistic studies of the hydrogenolysis of aryl ethers by nickel were undertaken with (diphosphine)aryl methyl ethers. A Ni(0) complex containing Ni-arene interactions adjacent to the aryl-O bond was isolated. Heating led to aryl-O bond activation and generation of a nickel aryl methoxide complex. Formal β-H elimination from this species produced a nickel aryl hydride which can undergo reductive elimination in the presence of formaldehyde to generate a carbon monoxide adduct of Ni(0). The reported complexes map out a plausible mechanism of aryl ether hydrogenolysis catalyzed by nickel. Investigations of a previously reported catalytic system using isotopically labeled substrates are consistent with the mechanism proposed in the stoichiometric system, involving β-H elimination from a nickel alkoxide rather than cleavage of the Ni-O bond by H(2).

Source: Journal of the American Chemical Society

DOI: 10.1021/ja300326t

Authors: Paul Kelley, Sibo Lin, Guy Edouard, Michael W. Day, Theodor Agapie

Institution: California Institute of Technology

Language: English

Topic: Organometallic Complex Synthesis and Catalysis

Subfield: Organic Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: green

Funder: National Center for Research Resources

Awards: 400 MHz Nuclear Magnetic Resonance Spectrometer, G7192793593