Heavier congeners of CO and CO2 as ligands: from zero-valent germanium ('germylone') to isolable monomeric GeX and GeX2 complexes (X = S, Se, Te)

dc.contributor.authorXiong, Yun
dc.contributor.authorYao, Shenglai
dc.contributor.authorKarni, Miriam
dc.contributor.authorKostenko, Arseni
dc.contributor.authorBurchert, Alexander
dc.contributor.authorApeloig, Yitzhak
dc.contributor.authorDrieß, Matthias
dc.date.accessioned2017-10-24T07:15:24Z
dc.date.available2017-10-24T07:15:24Z
dc.date.issued2016
dc.description.abstractIn contrast to molecular CO and CO2, their heavier mono- and dichalcogenide homologues, EX and EX2 (E = Si, Ge, Sn, Pb; X = O, S, Se, Te), are important support materials (e.g., SiO2) and/or semiconductors (e.g., SiS2) and exist typically as insoluble crystalline or amorphous polymers under normal conditions. Herein, we report the first successful synthesis and characterisation of an extraordinary series of isolable monomeric GeX and GeX2 complexes (X = S, Se, Te), representing novel classes of compounds and heavier congeners of CO and CO2. This could be achieved by solvent-dependent oxidation reactions of the new zero-valent germanium ('germylone')-GaCl3 precursor adduct (bis-NHC)Ge-0 -> GaCl3 1 (bis-NHC = H2C[{NC(H)=C(H)N(Dipp)}C:](2), Dipp = 2,6-iPr(2)C(6)H(3)) with elemental chalcogens, affording the donor-acceptor stabilised monomeric germanium(IV) dichalcogenide (bis-NHC)Ge-IV(=X)=X -> GaCl3 (X = S, 2; X = Se, 3) and germanium(II) monochalcogenide complexes (bis-NHC)Ge-II= X -> GaCl3 (X = Se, 4; X = Te, 5), respectively. Moreover, the reactivity of 4 and 5 towards elemental sulphur, selenium, and tellurium has been investigated. In THF, the germanium(II) monoselenide complex 4 reacts with activated elemental selenium to afford the desired germanium(IV) diselenide complex 3. Unexpectedly, both reactions of 4 and 5 with elemental sulphur, however, lead to the formation of germanium(IV) disulfide complex 2 under liberation of elemental Se and Te as a result of further oxidation of the germanium centre and replacement of the Se and Te atoms by sulphur atoms. All novel compounds 1-5 have been fully characterised, including single-crystal X-ray diffraction analyses, and studied by DFT calculations.en
dc.identifier.eissn2041-6539
dc.identifier.issn2041-6520
dc.identifier.urihttps://depositonce.tu-berlin.de//handle/11303/6899
dc.identifier.urihttp://dx.doi.org/10.14279/depositonce-6238
dc.language.isoen
dc.rights.urihttps://creativecommons.org/licenses/by/3.0/
dc.subject.ddc540 Chemie und zugeordnete Wissenschaftende
dc.titleHeavier congeners of CO and CO2 as ligands: from zero-valent germanium ('germylone') to isolable monomeric GeX and GeX2 complexes (X = S, Se, Te)en
dc.typeArticleen
dc.type.versionpublishedVersionen
dcterms.bibliographicCitation.doi10.1039/c6sc01839d
dcterms.bibliographicCitation.issue8
dcterms.bibliographicCitation.journaltitleChemical Scienceen
dcterms.bibliographicCitation.originalpublishernameRoyal Society of Chemistryde
dcterms.bibliographicCitation.originalpublisherplaceCambridgede
dcterms.bibliographicCitation.pageend5469
dcterms.bibliographicCitation.pagestart5462
dcterms.bibliographicCitation.volume7
tub.accessrights.dnbfree
tub.affiliationFak. 2 Mathematik und Naturwissenschaften>Inst. Chemie>FG Metallorganische Chemie und Anorganische Materialiende
tub.affiliation.facultyFak. 2 Mathematik und Naturwissenschaftende
tub.affiliation.groupFG Metallorganische Chemie und Anorganische Materialiende
tub.affiliation.instituteInst. Chemiede
tub.publisher.universityorinstitutionTechnische Universität Berlin
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