Ligand spheres in asymmetric hetero Diels-Alder reactions catalyzed by Cu(II) box complexes: experiment and modeling

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dc.contributor.authorUmamaheswari, V.
dc.contributor.authorCias, Pawel
dc.contributor.authorPöppl, Andreas
dc.contributor.authorKaupp, Martin
dc.contributor.authorGescheidt, Georg
dc.date.accessioned2016-06-22T08:05:23Z
dc.date.available2016-06-22T08:05:23Z
dc.date.issued2014
dc.descriptionDieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG geförderten) Allianz- bzw. Nationallizenz frei zugänglich.de
dc.descriptionThis publication is with permission of the rights owner freely accessible due to an Alliance licence and a national licence (funded by the DFG, German Research Foundation) respectively.en
dc.description.abstractThe stereoselective hetero Diels–Alder reaction between ethyl glyoxylate and cyclohexadiene catalyzed by [Cu(II)t-Bu-(box)](OTf)2 was investigated. The reaction was performed step-by-step and the geometry of the Cu(II) complexes formed in the course of the catalysis was analysed by EPR spectroscopy, advanced pulsed EPR methods (ENDOR, and HYSCORE) and DFT calculations. Our results show that one triflate counterion is directly coordinated to Cu(II) during the catalytic process (axial position). This leads to penta-coordinated Cu(II) complexes. Solvent molecules are able to alter the geometry of the Cu(II) complexes although their coordination is weak. These findings provide an explanation for the solvent and counterion effects observed in many catalytic reactions.en
dc.identifier.eissn1477-9226
dc.identifier.pmid24146076
dc.identifier.urihttps://depositonce.tu-berlin.de/handle/11303/5583
dc.identifier.urihttp://dx.doi.org/10.14279/depositonce-5212
dc.language.isoen
dc.rights.urihttp://rightsstatements.org/vocab/InC/1.0/en
dc.subject.ddc540 Chemie und zugeordnete Wissenschaftende
dc.titleLigand spheres in asymmetric hetero Diels-Alder reactions catalyzed by Cu(II) box complexes: experiment and modelingen
dc.typeArticleen
dc.type.versionpublishedVersionen
dcterms.bibliographicCitation.doi10.1039/c3dt51602d
dcterms.bibliographicCitation.issue2
dcterms.bibliographicCitation.journaltitleDalton transactions : a journal of inorganic chemistry, including bioinorganic, organometallic, and solid-state chemistryen
dcterms.bibliographicCitation.originalpublishernameRoyal Society of Chemistryde
dcterms.bibliographicCitation.originalpublisherplaceCambridgede
dcterms.bibliographicCitation.pageend705
dcterms.bibliographicCitation.pagestart698
dcterms.bibliographicCitation.volume43
tub.accessrights.dnbdomain
tub.affiliationFak. 2 Mathematik und Naturwissenschaften::Inst. Chemiede
tub.affiliation.facultyFak. 2 Mathematik und Naturwissenschaftende
tub.affiliation.instituteInst. Chemiede
tub.publisher.universityorinstitutionTechnische Universität Berlin

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