Changing the chemical and physical properties of high valent heterobimetallic bis-(mu-oxido) Cu-Ni complexes by ligand effects
dc.contributor.author | Kafentzi, Maria-Chrysanthi | |
dc.contributor.author | Orio, Maylis | |
dc.contributor.author | Réglier, Marius | |
dc.contributor.author | Yao, Shenglai | |
dc.contributor.author | Kuhlmann, Uwe | |
dc.contributor.author | Hildebrandt, Peter | |
dc.contributor.author | Drieß, Matthias | |
dc.contributor.author | Simaan, A. Jalila | |
dc.contributor.author | Ray, Kallol | |
dc.date.accessioned | 2017-10-24T07:15:09Z | |
dc.date.available | 2017-10-24T07:15:09Z | |
dc.date.issued | 2016 | |
dc.description.abstract | Two 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.sponsorship | DFG, EXC 314, Unifying Concepts in Catalysis | en |
dc.identifier.eissn | 1477-9234 | |
dc.identifier.issn | 1477-9226 | |
dc.identifier.pmid | 27509085 | |
dc.identifier.uri | https://depositonce.tu-berlin.de/handle/11303/6892 | |
dc.identifier.uri | http://dx.doi.org/10.14279/depositonce-6231 | |
dc.language.iso | en | |
dc.rights.uri | https://creativecommons.org/licenses/by/3.0/ | |
dc.subject.ddc | 540 Chemie und zugeordnete Wissenschaften | de |
dc.title | Changing the chemical and physical properties of high valent heterobimetallic bis-(mu-oxido) Cu-Ni complexes by ligand effects | en |
dc.type | Article | en |
dc.type.version | publishedVersion | en |
dcterms.bibliographicCitation.doi | 10.1039/c6dt02391f | |
dcterms.bibliographicCitation.issue | 40 | |
dcterms.bibliographicCitation.journaltitle | Dalton transactions | en |
dcterms.bibliographicCitation.originalpublishername | Royal Society of Chemistry | de |
dcterms.bibliographicCitation.originalpublisherplace | Cambridge | de |
dcterms.bibliographicCitation.pageend | 16000 | |
dcterms.bibliographicCitation.pagestart | 15994 | |
dcterms.bibliographicCitation.volume | 45 | |
tub.accessrights.dnb | free | |
tub.affiliation | Fak. 2 Mathematik und Naturwissenschaften::Inst. Chemie::FG Metallorganische Chemie und Anorganische Materialien | de |
tub.affiliation | Fak. 2 Mathematik und Naturwissenschaften::Inst. Chemie::FG Physikalische Chemie / Biophysikalische Chemie | de |
tub.affiliation.faculty | Fak. 2 Mathematik und Naturwissenschaften | de |
tub.affiliation.faculty | Fak. 2 Mathematik und Naturwissenschaften | de |
tub.affiliation.group | FG Metallorganische Chemie und Anorganische Materialien | de |
tub.affiliation.group | FG Physikalische Chemie / Biophysikalische Chemie | de |
tub.affiliation.institute | Inst. Chemie | de |
tub.affiliation.institute | Inst. Chemie | de |
tub.publisher.universityorinstitution | Technische Universität Berlin |
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