Changing the chemical and physical properties of high valent heterobimetallic bis-(mu-oxido) Cu-Ni complexes by ligand effects

dc.contributor.authorKafentzi, Maria-Chrysanthi
dc.contributor.authorOrio, Maylis
dc.contributor.authorRéglier, Marius
dc.contributor.authorYao, Shenglai
dc.contributor.authorKuhlmann, Uwe
dc.contributor.authorHildebrandt, Peter
dc.contributor.authorDrieß, Matthias
dc.contributor.authorSimaan, A. Jalila
dc.contributor.authorRay, Kallol
dc.date.accessioned2017-10-24T07:15:09Z
dc.date.available2017-10-24T07:15:09Z
dc.date.issued2016
dc.description.abstractTwo new heterobimetallic [LNiO2Cu(RPY2)](+) (RPY2 = N-substituted bis 2-pyridyl(ethylamine) ligands with R = indane, 3a or R = Me, 3b) complexes have been spectroscopically trapped at low temperatures. They were prepared by reacting the mononuclear side-on LNiII superoxo precursor bearing a beta-diketiminate ligand (L = [HC-(CMeNC6H3(iPr)(2))(2)]) with the Cu(I) complexes. In contrast to the oxo groups in known high-valent [M-2(mu-O)(2)](n+) (M = Fe, Co, Ni, Cu) cores that display electrophilic reactivities, 3a and 3b display rather nucleophilic oxo cores active in aldehyde deformylation reactions. However, the spectroscopic and reactivity properties of 3a/3b are found to be distinct relative to that of the previously reported [LNiO2Cu(MeAN)](+) complex containing a more basic (nucleophilic) N, N, N', N', N'-pentamethyl-dipropylenetriamine (MeAN) ligand at the copper centre. The geometry and electronic properties of the copper ligands affect the electron density of the oxygen atoms of the heterodinuclear {Ni(mu-O)(2)} core and 3a/3b undergo slower nucleophilic and faster electrophilic reactions than the previously reported [LNiO2Cu(MeAN)](+) intermediate. The present study therefore demonstrates the tuning of the electrophilicity/ nucleophilicity of the oxygen atoms of the heterobimetallic [Ni(mu-O)(2)Cu](2+) cores by controlling the electron donation from the ancillary ligands, and underlines the significance of subtle electronic changes in the physical and chemical properties of the biologically relevant heterobimetallic metal-dioxygen intermediates.en
dc.description.sponsorshipDFG, EXC 314, Unifying Concepts in Catalysisen
dc.identifier.eissn1477-9234
dc.identifier.issn1477-9226
dc.identifier.pmid27509085
dc.identifier.urihttps://depositonce.tu-berlin.de//handle/11303/6892
dc.identifier.urihttp://dx.doi.org/10.14279/depositonce-6231
dc.language.isoen
dc.rights.urihttps://creativecommons.org/licenses/by/3.0/
dc.subject.ddc540 Chemie und zugeordnete Wissenschaftende
dc.titleChanging the chemical and physical properties of high valent heterobimetallic bis-(mu-oxido) Cu-Ni complexes by ligand effectsen
dc.typeArticleen
dc.type.versionpublishedVersionen
dcterms.bibliographicCitation.doi10.1039/c6dt02391f
dcterms.bibliographicCitation.issue40
dcterms.bibliographicCitation.journaltitleDalton transactionsen
dcterms.bibliographicCitation.originalpublishernameRoyal Society of Chemistryde
dcterms.bibliographicCitation.originalpublisherplaceCambridgede
dcterms.bibliographicCitation.pageend16000
dcterms.bibliographicCitation.pagestart15994
dcterms.bibliographicCitation.volume45
tub.accessrights.dnbfree
tub.affiliationFak. 2 Mathematik und Naturwissenschaften>Inst. Chemie>FG Metallorganische Chemie und Anorganische Materialiende
tub.affiliationFak. 2 Mathematik und Naturwissenschaften>Inst. Chemie>FG Physikalische Chemie / Biophysikalische Chemiede
tub.affiliation.facultyFak. 2 Mathematik und Naturwissenschaftende
tub.affiliation.facultyFak. 2 Mathematik und Naturwissenschaftende
tub.affiliation.groupFG Metallorganische Chemie und Anorganische Materialiende
tub.affiliation.groupFG Physikalische Chemie / Biophysikalische Chemiede
tub.affiliation.instituteInst. Chemiede
tub.affiliation.instituteInst. Chemiede
tub.publisher.universityorinstitutionTechnische Universität Berlin
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