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Controlled Ring Opening of a Tetracyclic Tetraphosphane with Twofold Metallocene Bridging.
Dey, Subhayan; Szathmári, Balázs; Franz, Roman; Bruhn, Clemens; Kelemen, Zsolt; Pietschnig, Rudolf.
Afiliación
  • Dey S; Institut für Chemie und CINSaT, University of Kassel, Heinrich Plett-Straße 40, 34132, Kassel, Germany.
  • Szathmári B; Current address: School of Advanced Sciences, Vellore Institute of Technology, Vandalur-Kelambakkam Road, Rajan Nagar, Chennai, Tamil Nadu, 600127, India.
  • Franz R; Department of Inorganic and Analytical Chemistry, Budapest University of Technology and Economics, Muegyetem Rkp 3, 1111, Budapest, Hungary.
  • Bruhn C; Institut für Chemie und CINSaT, University of Kassel, Heinrich Plett-Straße 40, 34132, Kassel, Germany.
  • Kelemen Z; Institut für Chemie und CINSaT, University of Kassel, Heinrich Plett-Straße 40, 34132, Kassel, Germany.
  • Pietschnig R; Department of Inorganic and Analytical Chemistry, Budapest University of Technology and Economics, Muegyetem Rkp 3, 1111, Budapest, Hungary.
Chemistry ; 30(24): e202400194, 2024 Apr 25.
Article en En | MEDLINE | ID: mdl-38372413
ABSTRACT
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.
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Texto completo: 1 Colección: 01-internacional Base de datos: MEDLINE Idioma: En Revista: Chemistry Asunto de la revista: QUIMICA Año: 2024 Tipo del documento: Article País de afiliación: Alemania Pais de publicación: Alemania
Texto completo
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XML
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Texto completo: 1 Colección: 01-internacional Base de datos: MEDLINE Idioma: En Revista: Chemistry Asunto de la revista: QUIMICA Año: 2024 Tipo del documento: Article País de afiliación: Alemania Pais de publicación: Alemania