Die Reduktion von Triphenylphosphan-Derivaten zu ihren Radikalanionen und zum Dibenzophosphol-Radikaldianion [1]

The Reduction of Triphenylphosphane Derivatives to their Radical Anions and to the Radical Dianion of Dibenzophosphole [1]

  • Triphenylphosphane 1, its oxide 2 and sulfide 3 undergo one-electron reduction at a mercury cathode in DMF to yield the corresponding radical anions. ESE analysis of the paramagnetic species is facilitated by deuteration and suggests a pyramidal geometry of the radicals. Reduction with potassium metal in DME at low temperature yields also radical anions for 2 and 3. The phosphane 1, however, reacts under phenyl cleavage and potassiumphenyl-assisted ring closure to the dianion of 5H-dibenzophosphole 4. This radical 4· ⊖⊖ is also obtainod by alkali metal reduction of P-phenyldibenzophosphole o, and its spin distribution is compared to iso-.-π-electronic radicals containing CH, N, O, S, or Se links instead of the phosphorus atom.

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Metadaten
Author:Wolfgang KaimORCiDGND, Peter Hänel, Hans BockGND
URN:urn:nbn:de:hebis:30:3-417132
DOI:https://doi.org/10.1515/znb-1982-1104
ISSN:0175-0992
ISSN:0932-0776
Parent Title (German):Zeitschrift für Naturforschung. Teil B, Chemie, Biochemie, Biophysik, Biologie
Publisher:De Gruyter
Place of publication:Berlin [u.a.]
Document Type:Article
Language:German
Date of Publication (online):2016/10/24
Year of first Publication:1982
Publishing Institution:Universitätsbibliothek Johann Christian Senckenberg
Release Date:2016/10/24
Tag:Dibenzophosphole; ESR Spectra; Radicals; Reduction; Triphenylphosphane
Volume:37
Issue:11
Page Number:6
First Page:1382
Last Page:1387
Note:
© 1946 – 2014: Verlag der Zeitschrift für Naturforschung. This work is licensed under the Creative Commons Attribution-NonCommercial-NoDerivatives 3.0 License. (CC BY-NC-ND 3.0)
HeBIS-PPN:400089505
Institutes:Biochemie, Chemie und Pharmazie / Biochemie und Chemie
Dewey Decimal Classification:5 Naturwissenschaften und Mathematik / 54 Chemie / 540 Chemie und zugeordnete Wissenschaften
Sammlungen:Universitätspublikationen
Licence (German):License LogoCreative Commons - Namensnennung-Nicht kommerziell-Keine Bearbeitung 3.0