REACTIONS OF URANIUM TETRACHLORIDE WITH TERTIARY PHOSPHINES
Uranium tetrachloride forms solid addition compounds with the lower alcohols, but addition of a base to alcoholic solutions of UCl/sub 4/ promotes solvolysis by the removal of HCl. Addition of triphenylphosphine to a solution of UCl/sub 4/ in ethanol gives a precipitate of bis(triphenylphosphonium) hexachlorouranate (IV) (I), and quantitative yields are obtained on addition of concentrated HCl. Bis(triphenylphosphonium) hexachlorouranate(IV) is a green crystalline paramagnetic solid. Decomposition occurs above 180 deg and 2 equivalents of HCl are evolved consecutively with increasing temperature. Oxidation by air in boiling ethanol gives yellow crystalline bis(triphenylphosphonium) tetrachlorodioxouranate(VI) (II). Oxidation of an ethanol solution of UCl/sub 4/ and triphenylphosphine by chlorine gives green crystalline paramagnetic uranium tetrachloride -bis (triphenylphosphine oxide)(III). Further oxidation of tue compounds (II) and (III) gives yellow crystalline uranyl chloride-bis (triphenylphosphine oxide). Ethyldiphenylphosphine, diethylphenylphosphine, triethylphosphine, and tri-n- propylphosphine behave similarly. The phosphonium compounds show a P-H stretching band in the infrared region near 2420 cm/sup -1/, the uranyl compounds show a U = 0 stretching band at 920 cm/sup -1/, and the phosphine complexes show a P = 0 stretching band in the region 1050-1080 cm/sup -1/. (Uranium Abstr., Vol. 2; No. 5, July 1983)
- Research Organization:
- Univ. of London
- NSA Number:
- NSA-17-032064
- OSTI ID:
- 4693196
- Journal Information:
- Chemistry and Industry (London) (England), Vol. Vol: No. 22; Other Information: Orig. Receipt Date: 31-DEC-63
- Country of Publication:
- Country unknown/Code not available
- Language:
- English
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