secondary cells with lithium anodes and immobilized fused_salt

Compound
C102F
~ 1 , 0 ~ -146 ~
116.
TABU I11
PROPERTIES OF HALOGEN FLUORIDES AND DERIVATIVES
MP, OC BP, "C - NMR
-154 5
-76.3
-103 f 4
8.0
-60.5
8.5
4.85
above -115
4.5
- a Triple point 6.4.
,100.8
11.75
-14
127
40.0
97 .O
4 (1 atm.)
-6
-46.8
440
-14(a), -123(e)
-412(a), -247(e)
39
-132( e )
-53(a), -4(e)
-177 (-168)
-329 (330)
-287
- IR
793, 705
761, 746, 713, 694
706, 732, 541, 486
674, 613, 384, 300
683, 644, 587, 369
710, 640, 318 c
670, 547, 426, 368,
250
1270, 1255, 1104 (pqr)
632, 548
1315-1300, 725, 717,
714, 550
Chlorine trifluoride is usually described as having a T-shape, but is better
regarded as a trigonalbipyramid derivative. The two apical C1-F bonds are
elongated (1.70 1) compared to the equatorial C1-F bond (1.60 A). The bond angles
are 87.5' and 175'. The l9F NMR of gaseous CLF3 shows the apical fluorines to be
further downfield (-145.6 @) than the equatorial fluorine -19.7 @. In liquid ClF3
(with HF carefully removed) the resonances are -159.0 and -21.8 6. The high dipole
moment determined with the liquid (1.00-1.03 D) compared to that in the gas (- 0.6 D)
suggests corn iderable interaction and the relatively low volatility (b.p. 12') confirms
this, but the electrjcal conductivity shows that this interaction is essentially
not in the form of self-ionization to CLF2+ and ClF4- ions. Evidence for
some dimerization in the gas has been suggested. However stable salts of both of
these ions are known, e.g., Cp2+SbF6- and Cs+ClF4-. Chlorine trifluoride is commercially
available in quantity, being prepared by fluorination of chlorine. It is
an extremely vigorous fluorinating agent, but can in turn be fluorinated to ClF5
under pressure. Moisture converts CLF3 to C102F and C102. I
Chlorine pentafluoride is the newest member of the halogen fluoride family
and has very recently become available commercially in laboratory quantities. It is
prepared by the high pressure fluorination of ClF3 or a salt such as CsClF4 at 150'
or above. It has also been prepared by the fluorination of CLF3 under ultraviolet
radiation or electric discharge at low temperatures and by platinum hexafluoride.
The structure of CU5, a square pyramid, is an octahedral derivative with the apical
C1-F bond length of 1.62 1 and the equatorial bonds 1.72 A. The I9F chemical shifts
are -412 $ (apical fluorine) and -247 6 (basal fluorines). The former is one Of the
most unshielded fluorine atoms known, being exceeded only by those in F2, 02F2, and
NOF. The dipole moment is probably 0.2-0.4 D. The boiling point indicates very
little interaction exists in the liquid and self-ionization is not expected. The
C-4' ion is an intense peak in the mass spectrum and the possibility of obtaining
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