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dc.contributor.authorFrech Nabold, Christian M.-
dc.contributor.authorBlacque, Olivier-
dc.contributor.authorSchmalle, Helmut W.-
dc.contributor.authorBerke, Heinz-
dc.contributor.authorAdlhart, Christian-
dc.contributor.authorChen, Peter-
dc.date.accessioned2018-01-18T10:33:58Z-
dc.date.available2018-01-18T10:33:58Z-
dc.date.issued2006-04-12-
dc.identifier.issn0947-6539de_CH
dc.identifier.issn1521-3765de_CH
dc.identifier.urihttps://digitalcollection.zhaw.ch/handle/11475/2111-
dc.description.abstractThe reaction of [Re(H)(NO)2(PR3)2] complexes (1 a: R = PCy3; 1 b: R = PiPr3) with [H(OEt2)2][BArF4] ([BArF4] = tetrakis{3,5‐bis(trifluoromethyl)phenyl}borate) in benzene at room temperature gave the corresponding cations [Re(NO)2(PR3)2][BArF4] (2 a and 2 b). The addition of phenyldiazomethane to benzene solutions of 2 a and 2 b afforded the moderately stable cationic rhenium(I)‐benzylidene‐dinitrosyl‐bis(trialkyl)phosphine complexes 3 a and 3 b as [BArF4]− salts in good yields. The complexes 2 a and 2 b catalyze the ring‐opening metathesis polymerization (ROMP) of highly strained nonfunctionalized cyclic olefins to give polymers with relatively high polydispersity indices, high molecular weights and over 80 % Z configuration of the double bonds in the chain backbone. However, these complexes do not show metathesis activity with acyclic olefins. The benzylidene derivatives 3 a and 3 b are almost inactive in ROMP catalysis with norbornene and in olefin metathesis. NMR experiments gave the first hints of the initial formation of carbene complexes from [Re(NO)2(PR3)2][BArF4] (2 a and 2 b) and norbornene. In a detailed mechanistic study ESI‐MS/MS measurements provided further evidence that the carbene formation is initiated by a unique reaction sequence where the cleavage of the strained olefinic bond starts with phosphine migration forming a cyclic ylide–carbene complex, capable of undergoing metathesis with alternating rhenacyclobutane formation and cycloreversion reactions (“ylide” route). However, even at an early stage the ROMP propagation route is expected to merge into an “iminate” route by attack by the ylide function on one of the NNO atoms followed by phosphine oxide elimination. The formation of phosphine oxide was confirmed by NMR spectroscopy. The proposed mechanism is supported further by detailed DFT calculations.de_CH
dc.language.isoende_CH
dc.publisherWileyde_CH
dc.relation.ispartofChemistry - A European Journalde_CH
dc.rightsLicence according to publishing contractde_CH
dc.subjectReaction mechanismsde_CH
dc.subjectRing-opening polymerizationde_CH
dc.subjectDensity functional calculationsde_CH
dc.subjectMetathesisde_CH
dc.subject.ddc540: Chemiede_CH
dc.subject.ddc660: Technische Chemiede_CH
dc.titleUnprecedented ROMP activity of low-valent rhenium-nitrosyl complexes : mechanistic evaluation of an electrophilic olefin metathesis systemde_CH
dc.typeBeitrag in wissenschaftlicher Zeitschriftde_CH
dcterms.typeTextde_CH
zhaw.departementLife Sciences und Facility Managementde_CH
zhaw.organisationalunitInstitut für Chemie und Biotechnologie (ICBT)de_CH
zhaw.publisher.placeWeinheimde_CH
dc.identifier.doi10.1002/chem.200501025de_CH
zhaw.funding.euNode_CH
zhaw.issue12de_CH
zhaw.originated.zhawYesde_CH
zhaw.pages.end3338de_CH
zhaw.pages.start3325de_CH
zhaw.publication.statuspublishedVersionde_CH
zhaw.volume12de_CH
zhaw.publication.reviewPeer review (Publikation)de_CH
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Frech Nabold, C. M., Blacque, O., Schmalle, H. W., Berke, H., Adlhart, C., & Chen, P. (2006). Unprecedented ROMP activity of low-valent rhenium-nitrosyl complexes : mechanistic evaluation of an electrophilic olefin metathesis system. Chemistry - A European Journal, 12(12), 3325–3338. https://doi.org/10.1002/chem.200501025
Frech Nabold, C.M. et al. (2006) ‘Unprecedented ROMP activity of low-valent rhenium-nitrosyl complexes : mechanistic evaluation of an electrophilic olefin metathesis system’, Chemistry - A European Journal, 12(12), pp. 3325–3338. Available at: https://doi.org/10.1002/chem.200501025.
C. M. Frech Nabold, O. Blacque, H. W. Schmalle, H. Berke, C. Adlhart, and P. Chen, “Unprecedented ROMP activity of low-valent rhenium-nitrosyl complexes : mechanistic evaluation of an electrophilic olefin metathesis system,” Chemistry - A European Journal, vol. 12, no. 12, pp. 3325–3338, Apr. 2006, doi: 10.1002/chem.200501025.
FRECH NABOLD, Christian M., Olivier BLACQUE, Helmut W. SCHMALLE, Heinz BERKE, Christian ADLHART und Peter CHEN, 2006. Unprecedented ROMP activity of low-valent rhenium-nitrosyl complexes : mechanistic evaluation of an electrophilic olefin metathesis system. Chemistry - A European Journal. 12 April 2006. Bd. 12, Nr. 12, S. 3325–3338. DOI 10.1002/chem.200501025
Frech Nabold, Christian M., Olivier Blacque, Helmut W. Schmalle, Heinz Berke, Christian Adlhart, and Peter Chen. 2006. “Unprecedented ROMP Activity of Low-Valent Rhenium-Nitrosyl Complexes : Mechanistic Evaluation of an Electrophilic Olefin Metathesis System.” Chemistry - A European Journal 12 (12): 3325–38. https://doi.org/10.1002/chem.200501025.
Frech Nabold, Christian M., et al. “Unprecedented ROMP Activity of Low-Valent Rhenium-Nitrosyl Complexes : Mechanistic Evaluation of an Electrophilic Olefin Metathesis System.” Chemistry - A European Journal, vol. 12, no. 12, Apr. 2006, pp. 3325–38, https://doi.org/10.1002/chem.200501025.


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