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2021-05-20Zeitschriftenartikel DOI: 10.18452/25924
Mimicking of the histidine brace structural motif in molecular copper(I) compounds
dc.contributor.authorPeifer, Raphael
dc.contributor.authorMüller, Lars
dc.contributor.authorHoof, Santina
dc.contributor.authorBeckmann, Fabian
dc.contributor.authorCula, Beatrice
dc.contributor.authorLimberg, Christian
dc.date.accessioned2023-01-24T09:30:26Z
dc.date.available2023-01-24T09:30:26Z
dc.date.issued2021-05-20none
dc.identifier.urihttp://edoc.hu-berlin.de/18452/26614
dc.description.abstractL-Nτ-methylhistidine methyl ester, MeHisOMe, has been employed as a potential ligand to mimic the histidine brace-type coordination of copper ions in enzymes such as the particulate methane monoxygenase or lytic polysaccharide monooxygenases. MeHisOMe was prepared by double-methylation of histidine methyl ester. Subsequently, its complexation by diphosphine copper(I) precursors [Cu(P^P)(MeCN)2]BF4 was tested, which led to the complexes [Cu(P^P)(MeHisOMe)]BF4 (P^P=dpePhos: 1, P^P=XantPhos: 2, P^P=dppf: 3). 1–3 were fully characterized, also by single crystal X-ray analysis, thus providing first structural data for copper complexes with a synthetic, authentic histidine brace. The complexes proved inert in contact with dioxygen. To improve the biomimetic character attempts were made to formally replace the diphosphine ligands by bis(pyrazolyl)methanes, Bpm. Correspondingly, [BpmCu(NCMe)x]BF4 precursors were synthesized, with different substituents at the 3-positions of the pyrazolyl (i. e. Bpm=di(3-(phenyl)-1H-pyrazol-1-yl)diphenylmethane, di(3-(mesityl)-1H-pyrazol-1-yl)methane and di(3-(tert-butyl)-1H-pyrazol-1-yl)diphenylmethane). Addition of MeHisOMe to these complexes led to products that were so sensitive towards oxidation by the environment that they eluded isolation. One experiment provided blue crystals as a product of such a reaction. They belonged to a salt with a complex cation consisting of a Cu(μ-OH)2Cu core ligated by two MeHisOMe ligands, which dimerises in the solid state to give [Cu4(OH)4(MeHisOMe)4]4+.eng
dc.language.isoengnone
dc.publisherHumboldt-Universität zu Berlin
dc.rights(CC BY-NC-ND 4.0) Attribution-NonCommercial-NoDerivatives 4.0 Internationalger
dc.rights.urihttps://creativecommons.org/licenses/by-nc-nd/4.0/
dc.subjectcopper(I)eng
dc.subjecthistidine braceeng
dc.subjectbiomimeticeng
dc.subjectdiphosphineseng
dc.subjectbis(pyrazolyl)methaneeng
dc.subject.ddc540 Chemie und zugeordnete Wissenschaftennone
dc.titleMimicking of the histidine brace structural motif in molecular copper(I) compoundsnone
dc.typearticle
dc.identifier.urnurn:nbn:de:kobv:11-110-18452/26614-6
dc.identifier.doihttp://dx.doi.org/10.18452/25924
dc.type.versionpublishedVersionnone
local.edoc.pages8none
local.edoc.type-nameZeitschriftenartikel
local.edoc.container-typeperiodical
local.edoc.container-type-nameZeitschrift
dc.description.versionPeer Reviewednone
dc.identifier.eissn1521-3749
dcterms.bibliographicCitation.doi10.1002/zaac.202100145
dcterms.bibliographicCitation.journaltitleZeitschrift für anorganische und allgemeine Chemienone
dcterms.bibliographicCitation.volume847none
dcterms.bibliographicCitation.issue18none
dcterms.bibliographicCitation.originalpublishernameWiley-VCHnone
dcterms.bibliographicCitation.originalpublisherplaceWeinheimnone
dcterms.bibliographicCitation.pagestart1789none
dcterms.bibliographicCitation.pageend1796none
bua.departmentMathematisch-Naturwissenschaftliche Fakultätnone

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