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A COORDINATION MODEL AS AN ALTERNATIVE TO THE SOLVENT SYSTEM CONCEPT IN SOME OXYCHLORIDE SOLVENTS. I. SIMILARITY IN THE BEHAVIOR OF PHOSPHORUS OXYCHLORIDE AND TRIETHYL PHOSPHATE AS NON-AQUEOUS SOLVENTS

Journal Article · · Journal of the American Chemical Society (U.S.)
DOI:https://doi.org/10.1021/ja01482a004· OSTI ID:4834401

The solution behavior of anhydrous ferric chloride in triethyl phosphate STAPO(OEt)sub 3/! is shown to be very similar to the reported behavior of ferric chloride in phosphorus oxychloride. Spectral investigations demonstrate that the tetrachloroferrate (III) ion, STAFeCl/sub 4/!- on dissolution of ferric chloride in triethyl phosphate is a direct proof that ioniza-. tion of some FeCl/sub 3/ produces a cationic iron(III) species. This is interpreted as strong support for using a similar Lewis acid-base mechanism to explain the data in both POCl/sub 3/ and PO(OEt)/sub 3/. It is not necessary to obtain a chloride ion from the solvent POCl/sub 3/ to form STAFeCl/sub 4/!/sup -/. The equilibria shown are proposed to explain the behavior of ferric chloride in triethyl phosphate and to serve as an alternative to the solvent system explanation for phosphorus oxychloride solutions. FeCl/sub 3/ + Y/sub 3/PO -- STAFeCl/sub 3/OPY/sub 3/! in equilibrium 4/!/sup -/ in equilibrium STAFe(OPY/sub 3/)/sub n/!/sup 3+/ +

Research Organization:
Univ. of Illinois, Urbana
Sponsoring Organization:
USDOE
NSA Number:
NSA-16-001751
OSTI ID:
4834401
Journal Information:
Journal of the American Chemical Society (U.S.), Journal Name: Journal of the American Chemical Society (U.S.) Vol. Vol: 83; ISSN JACSA
Country of Publication:
Country unknown/Code not available
Language:
English