CaltechAUTHORS
  A Caltech Library Service

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

Kelley, Paul and Lin, Sibo and Edouard, Guy and Day, Michael W. and Agapie, Theodor (2012) Nickel-Mediated Hydrogenolysis of C–O Bonds of Aryl Ethers: What Is the Source of the Hydrogen? Journal of the American Chemical Society, 134 (12). pp. 5480-5483. ISSN 0002-7863. PMCID PMC3340012. https://resolver.caltech.edu/CaltechAUTHORS:20120507-081119603

[img] PDF - Accepted Version
See Usage Policy.

1791Kb
[img]
Preview
PDF - Supplemental Material
See Usage Policy.

2837Kb
[img] Crystallographic Info File (CIF) - Supplemental Material
See Usage Policy.

18Kb
[img] Crystallographic Info File (CIF) - Supplemental Material
See Usage Policy.

17Kb
[img] Crystallographic Info File (CIF) - Supplemental Material
See Usage Policy.

19Kb

Use this Persistent URL to link to this item: https://resolver.caltech.edu/CaltechAUTHORS:20120507-081119603

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.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/ja300326t DOIArticle
http://pubs.acs.org/doi/abs/10.1021/ja300326tPublisherArticle
https://www.ncbi.nlm.nih.gov/pmc/articles/PMC3340012/PubMed CentralArticle
ORCID:
AuthorORCID
Agapie, Theodor0000-0002-9692-7614
Additional Information:© 2012 American Chemical Society. Received: January 12, 2012. Published: March 6, 2012. We thank Lawrence M. Henling for crystallographic assistance. We are grateful to Caltech, BP, and NSF GRFP (S.L.) for funding. The Bruker KAPPA APEXII X-ray diffractometer was purchased via an NSF CRIF:MU award to Caltech, CHE- 0639094. The 400 MHz NMR spectrometer was purchased via an NIH award, RR027690.
Funders:
Funding AgencyGrant Number
CaltechUNSPECIFIED
BPUNSPECIFIED
NSF Graduate Research FellowshipUNSPECIFIED
NSFCHE-0639094
NIHRR027690
Issue or Number:12
PubMed Central ID:PMC3340012
Record Number:CaltechAUTHORS:20120507-081119603
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20120507-081119603
Official Citation:Nickel-Mediated Hydrogenolysis of C–O Bonds of Aryl Ethers: What Is the Source of the Hydrogen? Paul Kelley, Sibo Lin, Guy Edouard, Michael W. Day, and Theodor Agapie Journal of the American Chemical Society2012134 (12), 5480-5483
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:31321
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:08 May 2012 18:32
Last Modified:03 Oct 2019 03:50

Repository Staff Only: item control page