New Synthetic Procedures to Catena-Phosphorus Cations: Preparation and Dissociation of the First cyclo-Phosphino-halophosphonium Salts
Publikation: Beitrag in Fachzeitschrift › Forschungsartikel › Beigetragen › Begutachtung
Beitragende
Abstract
Chlorination of 1,2,3,4-tetracyclohexyl-cyclo-tetraphosphine (2) by PhICl2 or PCl5 in the presence of Me3SiOTf or GaCl3 provides a stepwise approach to salts of the first cyclo-phosphino-chlorophosphonium cations [Cy4P4Cl]+ ([19]+) and [Cy4P4Cl2]2+ ([20]2+). The analogous iodo derivative [Cy4P4I]+ ([17]+) is obtained as the tetraiodogallate salt from reaction of 2 with I2 in the presence of GaI3. Reactions of the dication [20]2+ with PMe3 or dmpe effect a dissociation of the cyclic framework resulting in the formation of salts containing [Me3PPCyPCyPMe3]2+ ([27]2+), [dmpeCyP]2+ ([29]2+), and [dmpeCyPCyP]2+ ([30]2+), respectively. The new cations represent phosphine complexes of the [PCy]2+ and [P2Cy2]2+ cationic fragments from [20]2+, demonstrating the coordinate nature of the phosphinophosphonium bonds in cyclo-phosphino-halophosphonium cations. The compounds have been characterized by NMR spectroscopy, single crystal X-ray crystallography, and Raman spectroscopy.
Details
Originalsprache | Englisch |
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Fachzeitschrift | Journal of the American Chemical Society |
Jahrgang | 2009 |
Publikationsstatus | Veröffentlicht - 2009 |
Peer-Review-Status | Ja |
Externe IDs
WOS | 000273028800046 |
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Scopus | 71749106331 |