Aufsatz
Budapesti Műszaki és Gazdaságtudományi Egyetem. Grant Number: Project UNKP-23-5-BME-419 and TKP2021-EGA-02; ZFF; Deutsche Forschungsgemeinschaft
Controlled Ring Opening of a Tetracyclic Tetraphosphane with Twofold Metallocene Bridging
Zusammenfassung
A 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.
Zitierform
In: Chemistry – A European Journal Volume 30 / Issue 24 (2024-02-19) eissn:1521-3765Förderhinweis
Gefördert im Rahmen des Projekts DEALBudapesti Műszaki és Gazdaságtudományi Egyetem. Grant Number: Project UNKP-23-5-BME-419 and TKP2021-EGA-02; ZFF; Deutsche Forschungsgemeinschaft
Zitieren
@article{doi:10.17170/kobra-2024052410192,
author={Dey, Subhayan and Szathmári, Balázs and Franz, Roman and Bruhn, Clemens and Kelemen, Zsolt and Pietschnig, Rudolf},
title={Controlled Ring Opening of a Tetracyclic Tetraphosphane with Twofold Metallocene Bridging},
journal={Chemistry – A European Journal},
year={2024}
}
0500 Oax 0501 Text $btxt$2rdacontent 0502 Computermedien $bc$2rdacarrier 1100 2024$n2024 1500 1/eng 2050 ##0##http://hdl.handle.net/123456789/15810 3000 Dey, Subhayan 3010 Szathmári, Balázs 3010 Franz, Roman 3010 Bruhn, Clemens 3010 Kelemen, Zsolt 3010 Pietschnig, Rudolf 4000 Controlled Ring Opening of a Tetracyclic Tetraphosphane with Twofold Metallocene Bridging / Dey, Subhayan 4030 4060 Online-Ressource 4085 ##0##=u http://nbn-resolving.de/http://hdl.handle.net/123456789/15810=x R 4204 \$dAufsatz 4170 5550 {{Ferrocen}} 5550 {{Ringerweiterung <Chemie>}} 5550 {{Chemische Bindung}} 5550 {{Aluminium}} 5550 {{Metallocene}} 7136 ##0##http://hdl.handle.net/123456789/15810
2024-06-03T15:07:24Z 2024-06-03T15:07:24Z 2024-02-19 doi:10.17170/kobra-2024052410192 http://hdl.handle.net/123456789/15810 Gefördert im Rahmen des Projekts DEAL Budapesti Műszaki és Gazdaságtudományi Egyetem. Grant Number: Project UNKP-23-5-BME-419 and TKP2021-EGA-02; ZFF; Deutsche Forschungsgemeinschaft eng Namensnennung 4.0 International http://creativecommons.org/licenses/by/4.0/ ferrocene cyclic oligophosphine regioselective ring-expansion P-catenation monovalent aluminum 540 Controlled Ring Opening of a Tetracyclic Tetraphosphane with Twofold Metallocene Bridging Aufsatz A 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. open access Dey, Subhayan Szathmári, Balázs Franz, Roman Bruhn, Clemens Kelemen, Zsolt Pietschnig, Rudolf doi:10.1002/chem.202400194 Grant Number: Project UNKP-23-5-BME-419 and TKP2021-EGA-02 Ferrocen Ringerweiterung <Chemie> Chemische Bindung Aluminium Metallocene publishedVersion eissn:1521-3765 Issue 24 Chemistry – A European Journal Volume 30 false e202400194
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