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dc.contributor.authorFrech, C. M.-
dc.contributor.authorBlacque, O.-
dc.contributor.authorSchmalle, H. W.-
dc.contributor.authorBerke, H.-
dc.date.accessioned2018-09-12T14:11:21Z-
dc.date.available2018-09-12T14:11:21Z-
dc.date.issued2006-
dc.identifier.issn1477-9226de_CH
dc.identifier.issn1477-9234de_CH
dc.identifier.urihttps://digitalcollection.zhaw.ch/handle/11475/10489-
dc.description.abstractThe addition of an excess of phenyldiazomethane to chlorobenzene solutions of the cationic dinitrosyl bisphosphine rhenium(-I) complexes [Re(NO)2(PR3)2][BAr(F)4] (R = Cy 1a, R = (i)Pr 1b) gave the corresponding benzylidene complexes [Re{=CH(C6H5)}(NO)2(PR3)2][BAr(F)4] (2a and 2b) in good yields. The treatment of 2b with dioxygen resulted in the oxidation of one of the nitrosyl ligands into the corresponding eta2-nitrito (3b) and nitrato complexes (4b) both in the solid state and in solution. In the case of the tricyclohexylphosphine derivative 2a the analogous conversion was not observed. A mechanism for the reaction of 2b with O2 is proposed which is based on an initial SET to the O2 molecule and subsequent formation of a peroxynitrite complex followed by the formation of a dinuclear mU-N2O4 intermediate. This in turn would undergo fission of the peroxo bond to afford 3b. A related sequence of steps is anticipated for the transformation of 3b to 4b. Furthermore, a similar mechanism seems reasonable for the seemingly topochemical reaction of 2b to 3b and 4b in the solid state. The initial SET to dioxygen and subsequent formation of the peroxynitrite complex is supported by DFT calculations on the trimethylphosphine model complexes [Re=CH{C6H5})(NO)2(PMe3)2]n+ (n = 1 and 2).de_CH
dc.language.isoende_CH
dc.publisherRoyal Society of Chemistryde_CH
dc.relation.ispartofDalton Transactionsde_CH
dc.rightsLicence according to publishing contractde_CH
dc.subject.ddc540: Chemiede_CH
dc.titleLigand controlled dioxygen oxidation of rhenium nitrosyl complexesde_CH
dc.typeBeitrag in wissenschaftlicher Zeitschriftde_CH
dcterms.typeTextde_CH
zhaw.departementLife Sciences und Facility Managementde_CH
dc.identifier.doi10.1039/b604858gde_CH
dc.identifier.pmid17016570de_CH
zhaw.funding.euNode_CH
zhaw.issue38de_CH
zhaw.originated.zhawNode_CH
zhaw.pages.end4598de_CH
zhaw.pages.start4590de_CH
zhaw.publication.statuspublishedVersionde_CH
zhaw.volume35de_CH
zhaw.publication.reviewPeer review (Publikation)de_CH
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Frech, C. M., Blacque, O., Schmalle, H. W., & Berke, H. (2006). Ligand controlled dioxygen oxidation of rhenium nitrosyl complexes. Dalton Transactions, 35(38), 4590–4598. https://doi.org/10.1039/b604858g
Frech, C.M. et al. (2006) ‘Ligand controlled dioxygen oxidation of rhenium nitrosyl complexes’, Dalton Transactions, 35(38), pp. 4590–4598. Available at: https://doi.org/10.1039/b604858g.
C. M. Frech, O. Blacque, H. W. Schmalle, and H. Berke, “Ligand controlled dioxygen oxidation of rhenium nitrosyl complexes,” Dalton Transactions, vol. 35, no. 38, pp. 4590–4598, 2006, doi: 10.1039/b604858g.
FRECH, C. M., O. BLACQUE, H. W. SCHMALLE und H. BERKE, 2006. Ligand controlled dioxygen oxidation of rhenium nitrosyl complexes. Dalton Transactions. 2006. Bd. 35, Nr. 38, S. 4590–4598. DOI 10.1039/b604858g
Frech, C. M., O. Blacque, H. W. Schmalle, and H. Berke. 2006. “Ligand Controlled Dioxygen Oxidation of Rhenium Nitrosyl Complexes.” Dalton Transactions 35 (38): 4590–98. https://doi.org/10.1039/b604858g.
Frech, C. M., et al. “Ligand Controlled Dioxygen Oxidation of Rhenium Nitrosyl Complexes.” Dalton Transactions, vol. 35, no. 38, 2006, pp. 4590–98, https://doi.org/10.1039/b604858g.


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