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Controlled Ring Opening of a Tetracyclic Tetraphosphane with Twofold Metallocene Bridging

dc.date.accessioned2024-06-03T15:07:24Z
dc.date.available2024-06-03T15:07:24Z
dc.date.issued2024-02-19
dc.identifierdoi:10.17170/kobra-2024052410192
dc.identifier.urihttp://hdl.handle.net/123456789/15810
dc.description.sponsorshipGefördert im Rahmen des Projekts DEALger
dc.description.sponsorshipBudapesti Műszaki és Gazdaságtudományi Egyetem. Grant Number: Project UNKP-23-5-BME-419 and TKP2021-EGA-02; ZFF; Deutsche Forschungsgemeinschaft
dc.language.isoeng
dc.rightsNamensnennung 4.0 International*
dc.rights.urihttp://creativecommons.org/licenses/by/4.0/*
dc.subjectferroceneeng
dc.subjectcyclic oligophosphineeng
dc.subjectregioselective ring-expansioneng
dc.subjectP-catenationeng
dc.subjectmonovalent aluminumeng
dc.subject.ddc540
dc.titleControlled Ring Opening of a Tetracyclic Tetraphosphane with Twofold Metallocene Bridgingeng
dc.typeAufsatz
dcterms.abstractA direct route to a doubly ferrocene bridged tetracyclic tetraphosphane 1 was developed via reductive coupling of Fe(CpPCl₂)₂ (2 a), where a chlorine terminated linear P₄-compound 3 could be identified as an intermediate. Selective P−P bond activation was further achieved by reacting 1 with elemental selenium or [Cp*Al]₄, where regioselective insertion of Se or Al atoms resulted in ferrocenylene bridged [P₄Se] (4) or [P₄Al] (7) moieties. Compound 7 can be transformed to a hydrogen terminated linear P₄ species, 8, with protic solvents. Methylation of compound 1 with MeOTf, proceeds via intermediate formation of monomethylated species 5, which gradually produced Me₂-terminated dicationic 6, again containing a linear P₄-unit. Besides spectroscopic characterization, the structural details of compounds 1, 4, 6, and 8 could be determined by SC-XRD. Moreover, DFT calculations were used to rationalize the reactivity of 1, derived compounds and intermediates. As a key feature, 1 undergoes ring opening polymerization to a linear polyphosphane 9.eng
dcterms.accessRightsopen access
dcterms.creatorDey, Subhayan
dcterms.creatorSzathmári, Balázs
dcterms.creatorFranz, Roman
dcterms.creatorBruhn, Clemens
dcterms.creatorKelemen, Zsolt
dcterms.creatorPietschnig, Rudolf
dc.relation.doidoi:10.1002/chem.202400194
dc.relation.projectidGrant Number: Project UNKP-23-5-BME-419 and TKP2021-EGA-02
dc.subject.swdFerrocenger
dc.subject.swdRingerweiterung <Chemie>ger
dc.subject.swdChemische Bindungger
dc.subject.swdAluminiumger
dc.subject.swdMetalloceneger
dc.type.versionpublishedVersion
dcterms.source.identifiereissn:1521-3765
dcterms.source.issueIssue 24
dcterms.source.journalChemistry – A European Journaleng
dcterms.source.volumeVolume 30
kup.iskupfalse
dcterms.source.articlenumbere202400194


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