for experimental assistance.reflux for 12 hr. The reaction mixture was then concentrated by removing toluene under ca. 20 mm pressure at room temperature, when the product crystallized out as white needle crystals. These were purified as in part xxiib and were shown to be identical with XXIVa. [AlMe,] (XXV). The procedure was as in part xxiib using XXVI (1.40 g, 0.01 mol) with AlMe, (0.96 ml, 0.01 mol) in 5 ml of toluene. Colorless needle crystals were obtained. Anal. Calcd for C,H,,S-NaA1,: Al, 25.5; (Et t Me):Al ratio, 2.5; Me:Et ratio, 1.50. Found: Al, 25.0; (Et t Me):Al ratio, 2.4; Me:Et ratio, 1.48. (xxv) Dissociation of XXIV. (a) The complex XXIV (ca. 5 g)was washed five times with 10-ml portions of n-hexane at O", and 15 ml of toluene was then added. This dissolved nearly all of the solid, and the undissolved residue (cu. 0.1 g) was identified as XXVI.(b) XXIV (ca. 2 g) was dissolved in toluene (10 ml), and the solution was allowed to stand for 1 week in a sealed tube at room temperature. During this time a white solid was deposited (ca. 0.2 g) which was identified as XXVI.(xxiv) Diethyltrimethyldialuminum Sodiosulfide, [Et, AISNa] -(c) On heating pure XXIV above 50", it gradually decomposed.Infrared spectra were obtained with a Nihon Bunko far-infrared GC-402G instrument, using a compensation technique with a variablespacing cell. Nmr spectra were measured on a Varian A-60 instrument at room temperature.Registry No. AlMe,, AlEt,,,, 100-99-

A number of dialkyltin(1V)-bisfluorosulfates, -bistrifluoromethanesulfonates, and -bisdifluorophosphates are synthesized by solvolysis of dialkyltin(1V) chlorides in an excess of the corresponding acid according to 25 "C R2SnC12 + 2HX-R2SnX2 + 2HCI; R = CH,, C2H5, n-C3H7, n-C4Hg, and tl-C,H17 ; X = SO,F, SO,CF,, and P02F2. The structural proposals, hexacoordination for tin with the alkyl groups in trans-octahedral position and bidentate bridging anionic groups with coordination through oxygen, are based on l19Sn Mossbauer, infrared and, where obtainable, Raman spectra. The vibrational spectra of the difluorophosphates are discussed in detail. Variations in isomer shift and quadrupole splitting values with different alkyl groups in all three groups of compounds follow the same regular pattern as in the series R2SnF2. 0- L3

The interaction of the monobasic protonic acids H S 0 3 F , HS03CH3, H P 0 2 F 2 , and HCOzCF3 with titanium(1V) chloride at room temperature is studied with either the acid or the metal halide in excess. Whereas with the acid in excess products of the type TiCI2Y2, with Y = oxyacid group, are formed, the excess of TiCI, results in the formation of TiC13.33(S03F)o.66, TiC13S03CH3, and again TiC12(P02F2)2 and TiC12(C02CF3),.The first two compounds are also obtained by ligand redistribution reactions with TiCI, in excess, e.g.in quantitative yield. Vibrational spectra for the P02F2, S 0 3 F and the previously reported S 0 3 C F 3 derivatives are interpreted in terms of hexacoordinated titanium and generally bi-or tridentate oxyacid groups. In TiC13.33(S03F)o.66 evidence for a highly unusual tetradentate S 0 3 F group is presented, where coordination to titanium involves all three oxygens as well as fluorine.L'interaction des acides protoniques monobasiques, H S 0 3 F , HS03CH3, H P 0 2 F 2 et H C 0 2 C F 3 avec le chlorure de titane(1V) a t t t etudite a temptrature ambiante en employant soit I'acide, soit I'halogtnure mttallique en excts.Lorsque l'acide est en excts, on note la formation de produits du type TiC12Y2 ou Y = groupe oxyacide; par contre, I'exces de TiCI, conduit a la formation de TiC13.33(S03F)0.66, de TiCI3SO3CH3, deLes deux premiers composts sont aussi obtenus quantitativement a I'aide de reactions de redistribution du coordinat en prtsence d'un excis de TiCI,, e.g. 25 "C TiC12(S03CH3)2 + TiCI4 + 2TiC13S03CH3Les spectres de vibration des dtrivts P02F2-, S03F-et S03CF3-, lequel a dtja ett rapportt. sont interprttts en fonction de titanium hexacoordonne et de groupes oxyacides gtneralement bi ou tricoordonnts. Dans le TiC13.33(S03F)o.66, on met en tvidence la prtsence d'un groupe S 0 3 F tetracoordonnt assez inhabituel oh la coordination du titanium implique les trois oxygenes ainsi q u e le fluor.[Traduit par le journal]Can. J. Chern., 52, 231 (1974)

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