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1,2‐Diphosphole and 1,4,7,10‐Tetraphosphaphenalene Derivatives from the Reaction of Allylidenetriphenylphosphorane and PCl 3
Author(s) -
Breitsameter Florian,
Polborn Kurt,
Schmidpeter Alfred
Publication year - 1998
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/(sici)1099-0682(199812)1998:12<1907::aid-ejic1907>3.0.co;2-m
Subject(s) - chemistry , disproportionation , crystal structure , phosphorus trichloride , ionic bonding , ring (chemistry) , ionic liquid , medicinal chemistry , chloride , ion , nuclear magnetic resonance spectroscopy , crystallography , stereochemistry , inorganic chemistry , organic chemistry , catalysis
The equation 7 1 + 11 PCl 3 → 2 7 + 11 + 21 HCl describes in part the reaction of allylidenetriphenylphosphorane (triphenylphosphonium allylide) 1 with PCl 3 . It involves the substitution of all α‐ and γ‐hydrogen atoms of 1 and a concomitant disproportionation of the phosphorus. The reduction product 11 and its less highly substituted precursor 9 are new examples of the favoured family of 3‐phosphonio 1,2‐diphospholides and 1,2,4‐triphospholides. The cation of the ionic oxidation product 7 has a phenalene structure with three peripheric PCl ring members and a chlorophosphonium center. In the crystal two of these bowl‐shaped cations encapsulate a chloride anion. This is shown by an X‐ray structure investigation. The structure of other products is elucidated by 31 P‐NMR spectroscopy.