Cu(I)-Amido Complexes in the Ullmann Reaction: Reactions of Cu(I)-Amido Complexes with lodoarenes with and without Autocatalysis by CuI.
A series of Cu(I)-amido complexes both lacking ancillary ligands and containing 1,10-phenanthroline (phen) as ancillary ligand have been prepared. These complexes react with iodoarenes to form arylamine products, and this reactivity is consistent with the intermediacy of such complexes in catalytic...
| Publicado en: | Journal of the American Chemical Society Vol. 132; no. 45; pp. 15860 - 15864 |
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| Autores principales: | , |
| Formato: | Artículo |
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American Chemical Society
11/17/2010
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| Acceso en línea: | Ver este registro en EBSCOhost |
| fields | @attributes: recordID: 1 pdfLink: plink: https://search.ebscohost.com/login.aspx?direct=true&db=hlh&AN=55426455&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 55426455 longDbName: Humanities International Complete uiTag: AN controlInfo: bkinfo: jinfo: jid: 00027863 ACS jtl: Journal of the American Chemical Society issn: 00027863 maglogo: N pubinfo: dt: 11/17/2010 vid: 132 iid: 45 pid: 997 pub: American Chemical Society artinfo: ui: 55426455 10.1021/ja105695s ppf: 15860 ppct: 4 formats: tig: atl: Cu(I)-Amido Complexes in the Ullmann Reaction: Reactions of Cu(I)-Amido Complexes with lodoarenes with and without Autocatalysis by CuI. aug: au: Giri, Ramesh Hartwig, John F. affil: Department of Chemistry, University of Illinois, 600 South Mathews Avenue, Urbana, Illinois 61801, United States su: Reactivity (Chemistry) Complex compounds Copper Autocatalysis Halides Density functionals Oxidative stress sug: subj: Reactivity (Chemistry) Complex compounds Copper Autocatalysis Halides Density functionals Oxidative stress ab: A series of Cu(I)-amido complexes both lacking ancillary ligands and containing 1,10-phenanthroline (phen) as ancillary ligand have been prepared. These complexes react with iodoarenes to form arylamine products, and this reactivity is consistent with the intermediacy of such complexes in catalytic Ullmann amination reactions. The stoichiometric reactions of the Cu(I)-amido complexes with iodoarenes are autocatalytic, with the free CuI generated during the reaction serving as the catalyst. Such autocatalytic behavior was not observed for reactions of iodoarenes with copper(I) amidates, imidates, or phenoxides. The selectivity of these complexes for two sterically distinct aryl halides under various conditions imply that the autocatalytic reaction proceeds by forming highly reactive [CuNPh] lacking phen. Reactions with radical probes imply that the reactions of phen-ligated Cu(I)-amido complexes with iodoarenes occur without the intermediacy of aryl radicals. Density functional theory calculations on the oxidative addition of lodoarenes to Cu(I) species are consistent with faster reactions of iodoarenes with CuNPh species lacking phen in DMSO than reactions of iodoarenes with LCuNPh in which L = phen. The free-energy barrier computed for the reaction of PhI with (DMSO)CuNPh was 21.8 kcaVmol, while that for the reaction of PhI with (phen)CuNPh was 33.4 kcaVmol. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2010 holdings: @attributes: islocal: N |
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