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dc.contributor.authorFrech, Christian M.-
dc.contributor.authorMilstein, David-
dc.date.accessioned2018-09-13T06:52:52Z-
dc.date.available2018-09-13T06:52:52Z-
dc.date.issued2006-
dc.identifier.issn0002-7863de_CH
dc.identifier.issn1520-5126de_CH
dc.identifier.urihttps://digitalcollection.zhaw.ch/handle/11475/10513-
dc.description.abstractA rare case of directly observed alkyl halide reductive elimination from rhodium is reported. Treatment of the naphthyl-based PCP-type Rh(III) methyl complexes 2a,b [(C10H5(CH2PR2)2)Rh(CH3)(I)] (R = iPr 2a, R = tBu 2b) with CO resulted in facile reductive elimination of methyl iodide in the case of 2b, yielding the Rh(I) carbonyl complex [(C10H5(CH2PR2)2)Rh(CO)] 3b (R = tBu), while the less bulky 2a formed CO adducts and did not undergo reductive elimination, contrary to expectations based on electron density considerations. Moreover, 3b oxidatively added methyl iodide, while 3a did not. CD3I/CH3I exchange studies in the absence of CO indicate that reversible formation of (ligated) methyl iodide takes place in both systems. Subsequently, when CO is present, it displaces methyl iodide in the bulkier tBu system, whereas with the iPr system formation of the Rh(III) CO adducts is favored. Iodide dissociation followed by its attack on the rhodium-methyl group is unlikely.de_CH
dc.language.isoende_CH
dc.publisherAmerican Chemical Societyde_CH
dc.relation.ispartofJournal of the American Chemical Societyde_CH
dc.rightsLicence according to publishing contractde_CH
dc.subject.ddc540: Chemiede_CH
dc.titleDirect observation of reductive elimination of methyl iodide from a rhodium(III) pincer complex : the importance of stericsde_CH
dc.typeBeitrag in wissenschaftlicher Zeitschriftde_CH
dcterms.typeTextde_CH
zhaw.departementLife Sciences und Facility Managementde_CH
dc.identifier.doi10.1021/ja064945dde_CH
dc.identifier.pmid16984191de_CH
zhaw.funding.euNode_CH
zhaw.issue38de_CH
zhaw.originated.zhawNode_CH
zhaw.pages.end12435de_CH
zhaw.pages.start12434de_CH
zhaw.publication.statuspublishedVersionde_CH
zhaw.volume128de_CH
zhaw.publication.reviewPeer review (Publikation)de_CH
Appears in collections:Publikationen Life Sciences und Facility Management

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Frech, C. M., & Milstein, D. (2006). Direct observation of reductive elimination of methyl iodide from a rhodium(III) pincer complex : the importance of sterics. Journal of the American Chemical Society, 128(38), 12434–12435. https://doi.org/10.1021/ja064945d
Frech, C.M. and Milstein, D. (2006) ‘Direct observation of reductive elimination of methyl iodide from a rhodium(III) pincer complex : the importance of sterics’, Journal of the American Chemical Society, 128(38), pp. 12434–12435. Available at: https://doi.org/10.1021/ja064945d.
C. M. Frech and D. Milstein, “Direct observation of reductive elimination of methyl iodide from a rhodium(III) pincer complex : the importance of sterics,” Journal of the American Chemical Society, vol. 128, no. 38, pp. 12434–12435, 2006, doi: 10.1021/ja064945d.
FRECH, Christian M. und David MILSTEIN, 2006. Direct observation of reductive elimination of methyl iodide from a rhodium(III) pincer complex : the importance of sterics. Journal of the American Chemical Society. 2006. Bd. 128, Nr. 38, S. 12434–12435. DOI 10.1021/ja064945d
Frech, Christian M., and David Milstein. 2006. “Direct Observation of Reductive Elimination of Methyl Iodide from a rhodium(III) Pincer Complex : The Importance of Sterics.” Journal of the American Chemical Society 128 (38): 12434–35. https://doi.org/10.1021/ja064945d.
Frech, Christian M., and David Milstein. “Direct Observation of Reductive Elimination of Methyl Iodide from a rhodium(III) Pincer Complex : The Importance of Sterics.” Journal of the American Chemical Society, vol. 128, no. 38, 2006, pp. 12434–35, https://doi.org/10.1021/ja064945d.


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