The preparation of the complexes ( w -C ~H ~) & ~L ,

19F nuclear magnetic resonance (n.m.r.) studies show that SbF5 forms HSbF,(OOCCF,) in trifluoroacetic acid. This complex acid does not react with (CF3CO)20 which must be added to carry out conductimetric studies in anhydrous HOOCCF3. However, HCIO.,, HS03F, and HNO, all react with (CF3CO)Z0 to yield mixed anhydrides CF3COC104, CF3COS03F, and N0200CCF3. HBF., reacts with the anhydride to give CF3COF while HZS04 appears to be simply dehydrated to polysulfuric acids.

The preparation and properties of the 2-mercaptoethylamino-and o-aminothiophenolate derivatives, [ (~T-C,H,)~-MNH,(CH,),S]+X-and (n-C5H5),MNHC6H4S (M = M o or W) and [ ( ~T -C ~H ~) ~W N H ~C ~H ~S ] + C I -are reported. Similarly the o-aminophenolate, acetylacetonato-and 9.1 0-anthraquinone complexes (T-C~H~),MONHC~H,O, [(T-C~H~),MOO,C~H,] +X-, and ( T -C ~H ~) , W O , C ~~H ~ are described. The complexes have been characterised by analysis and l H n.m.r., i.r., and, in some cases, mass spectroscopy.

The limiting equivalent conductivities, Λ0, of the acids, HB(OOCCF3)4 and HSbF5(OOCCF3), and the salt, CsB(OOCCF3)4, have been measured and found to be 22.34, 18.77, and 48.56 ohm−1 cm2 equiv−1, respectively. Calculation of the solvent autoprotolysis constant gives the value: 4 × 10−14 mol2 l−2. The salt, CsB(OOCCF3)4 is readily prepared but the parent acid, B(OOCCF3)3 could not be isolated.

Electrolytes studied in 100'j/, trifluoroacetic acid exhibit a minimum in equivalent conductivity with increasing solute concentration. This behavior is accounted for by the formation of triple-ions at higher concentrations. Triple-ion dissociation constants, k , have been evaluated and, in general, they show the opposite trend with changing ion size to that of the ion-pair dissociation constants; that is the triple-ions of smaller ions are more dissociated. The experimentally observed trend is accounted for by using a partial ionic charge instead of unit charge for the ion-pair charges in the theoretical Fuoss expression for k .The excellent extrapolation of the triple-ion data to give a value of A°Kd for the ion-pair, which agrees well with that determined from a Fuoss plot, permits an estimate of A0 for LiO,CCF, from the triple-ion data.Les electrolytes etudies dans I'acide trifluoroacetique a 100% montrent un minimum, i conductivite tquivalente, pour une concentration croissante en solute. Ce phtnomine s'explique par la formation d'ions triples en concentrations elevees. Les constantes de dissociation des ions triples k ont ete evaluees; elles varient generalement en sens contraire, par rapport aux constantes de dissociation des paires d'ions, avec le changement dans la taille de l'ion. Cette tendance, observee experimentalement, a ete interpretee en utilisant une charge ionique partielle, au lieu de l'unite pour les charges des paires d'ions dans I'expression thtorique de Fuoss pour k.L'excellente extrapolation des donntes sur I'ion triple pour la valeur A°Kd de la paire d'ion, en bon accord avec la valeur tiree de la courbe de Fuoss, permet une estimation de A0 pour LiO,CCF, a partir des donnees sur I'ion triple.