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dc.contributor.authorJiang, Yanfeng-
dc.contributor.authorBlacque, Olivier-
dc.contributor.authorFox, Thomas-
dc.contributor.authorFrech, Christian M.-
dc.contributor.authorBerke, Heinz-
dc.date.accessioned2018-09-12T12:49:49Z-
dc.date.available2018-09-12T12:49:49Z-
dc.date.issued2010-
dc.identifier.issn0947-6539de_CH
dc.identifier.issn1521-3765de_CH
dc.identifier.urihttps://digitalcollection.zhaw.ch/handle/11475/10471-
dc.description.abstractThe five-coordinated Re(I) hydride complexes [Re(Br)(H)(NO)(PR(3))(2)] (R=Cy 1 a, iPr 1 b) were reacted with benzylbromide, thereby affording the 17-electron mononuclear Re(II) hydride complexes [Re(Br)(2)(H)(NO)(PR(3))(2)] (R=Cy 3 a, iPr 3 b), which were characterized by EPR, cyclic voltammetry, and magnetic susceptibility measurements. In the case of dibromomethane or bromoform, the reaction of 1 afforded Re(II) hydrides 3 in addition to Re(I) carbene hydrides [Re(=CHR(1))(Br)(H)(NO)(PR(3))(2)] (R(1)=H 4, Br 5; R=Cy a, iPr b) in which the hydride ligand is positioned cis to the carbene ligand. For comparison, the dihydrogen Re(I) dibromide complexes [Re(Br)(2)(NO)(PR(3))(2)(eta(2)-H(2))] (R=Cy 2 a, iPr 2 b) were reacted with allyl- or benzylbromide, thereby affording the monophosphine Re(II) complex salts [R(3)PCH(2)R'][Re(Br)(4)(NO)(PR(3))] (R'=-CH=CH(2) 6, Ph 7). The reduction of Re(II) complexes has also been examined. Complex 3 a or 3 b can be reduced by zinc to afford 1 a or 1 b in high yield. Under catalytic conditions, this reaction enables homocoupling of benzylbromide (turnover frequency (TOF): 3 a 150, 3 b 134 h(-1)) or allylbromide (TOF: 3 a 575, 3 b 562 h(-1)). The reaction of 6 a and 6 b with zinc in acetonitrile affords in good yields the monophosphine Re(I) complexes [Re(Br)(2)(NO)(MeCN)(2)(PR(3))] (R=Cy 8 a, iPr 8 b), which showed high catalytic activity toward highly selective dehydrogenative silylation of styrenes (maximum TOF of 61 h(-1)). Single-electron transfer (SET) mechanisms were proposed for all these transformations. The molecular structures of 3 a, 6 a, 6 b, 7 a, 7 b, and 8 a were established by single-crystal X-ray diffraction studies.de_CH
dc.language.isoende_CH
dc.publisherWileyde_CH
dc.relation.ispartofChemistry - A European Journalde_CH
dc.rightsLicence according to publishing contractde_CH
dc.subject.ddc540: Chemiede_CH
dc.titleFacile synthetic access to rhenium(II) complexes : activation of carbon-bromine bonds by single-electron transferde_CH
dc.typeBeitrag in wissenschaftlicher Zeitschriftde_CH
dcterms.typeTextde_CH
zhaw.departementLife Sciences und Facility Managementde_CH
dc.identifier.doi10.1002/chem.200902600de_CH
dc.identifier.pmid20066700de_CH
zhaw.funding.euNode_CH
zhaw.issue7de_CH
zhaw.originated.zhawNode_CH
zhaw.pages.end2249de_CH
zhaw.pages.start2240de_CH
zhaw.publication.statuspublishedVersionde_CH
zhaw.volume16de_CH
zhaw.publication.reviewPeer review (Publikation)de_CH
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Jiang, Y., Blacque, O., Fox, T., Frech, Christian M., & Berke, H. (2010). Facile synthetic access to rhenium(II) complexes : activation of carbon-bromine bonds by single-electron transfer. Chemistry - A European Journal, 16(7), 2240–2249. https://doi.org/10.1002/chem.200902600
Jiang, Y. et al. (2010) ‘Facile synthetic access to rhenium(II) complexes : activation of carbon-bromine bonds by single-electron transfer’, Chemistry - A European Journal, 16(7), pp. 2240–2249. Available at: https://doi.org/10.1002/chem.200902600.
Y. Jiang, O. Blacque, T. Fox, Christian M. Frech, and H. Berke, “Facile synthetic access to rhenium(II) complexes : activation of carbon-bromine bonds by single-electron transfer,” Chemistry - A European Journal, vol. 16, no. 7, pp. 2240–2249, 2010, doi: 10.1002/chem.200902600.
JIANG, Yanfeng, Olivier BLACQUE, Thomas FOX, Christian M. FRECH und Heinz BERKE, 2010. Facile synthetic access to rhenium(II) complexes : activation of carbon-bromine bonds by single-electron transfer. Chemistry - A European Journal. 2010. Bd. 16, Nr. 7, S. 2240–2249. DOI 10.1002/chem.200902600
Jiang, Yanfeng, Olivier Blacque, Thomas Fox, Christian M. Frech, and Heinz Berke. 2010. “Facile Synthetic Access to rhenium(II) Complexes : Activation of Carbon-Bromine Bonds by Single-Electron Transfer.” Chemistry - A European Journal 16 (7): 2240–49. https://doi.org/10.1002/chem.200902600.
Jiang, Yanfeng, et al. “Facile Synthetic Access to rhenium(II) Complexes : Activation of Carbon-Bromine Bonds by Single-Electron Transfer.” Chemistry - A European Journal, vol. 16, no. 7, 2010, pp. 2240–49, https://doi.org/10.1002/chem.200902600.


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