ISSN:
0009-2940
Keywords:
Phase-transfer catalysis
;
Ozonides, ionic
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Synthetic Routes to New Ionic OzonidesNew synthetic routes to tetraorganylammonium ozonides involving exchange reactions with alkali metal ozonides were investigated. The previously reported reaction between tetraalkylammonium hyperoxides R4N+O2- (R = Me, Et) and alkali metal ozonides in liquid ammonia is severely hampered by the difficult synthesis of these hyperoxides; they are unknown for other quaternary ammonium cations. A similar reaction between the easily accessible chlorides of trialkylbenzylammonium ions and KO3 yields mixed ozonides/chlorides due to some solubility of KCl in liquid ammonia. The new compounds BzlMe3N+ (O3-)0.6Cl-0.4 (3), BzlEt3N+ (O3-)0.8Cl0.2- (4) and Bzl(nBu)3N+(O3-)0.5Cl0.5- (5) were prepared by this route. - The by far superior route to new ozonides utilizes macroreticular cation exchange resins in liquid ammonia. Batch equilibration between an excess of the appropriate ionic form of the resin and CsO3 produced Me3PhN+O3- (6), BzlMe3N+O3- (7), Bzl(nBu)3N+O3- (8), and (nPr)4N+ O3- (9) in almost quantitative yield. Compounds 4, 6, and 7 were studied by single-crystal X-ray analysis; the shortening of the ozonide bond length and the widening of the bond angle in comparison to the alkali metal ozonides as well as the possibility of C-H…O hydrogen bonding are discussed. Thermal stabilities were determined by DTA/TG methods, rapid decomposition starts at 59-79°C for 3, 6, and 7 and at 28-56°C for the remaining new ozonides which contain detachable β-H atoms.
Additional Material:
3 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19921250613
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