Titanium(IV) Chloro-Derivatives of Strong Monobasic Acids

Abstract

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)

Coordinated trifluoromethanesulfonate and fluorosulfate

“…Crystallography indicates exclusively O-bonding; there is no structural evidence for participation of the fluorine atom on FS03in bonding, although this possibility has been raised on at least one occasion. 78 In all cases where covalency occurs in the structure, the situation is clear-cut; for example, the (jLt-fluorosulfato)bis(fluoroxenon(II)) cation has a Xe-0 bond of 2.21 A, far too short to support only ionic interactions since the purely ionic (van der Waals contact) distance would be 3.7 A in that case.79 Nevertheless, particularly with transition-metal compounds, M-0 distances for coordinated RS03are longer than usual M-0 distances, indicative of the low degree of nucleophilicity of these ions. For example, the Fe(I-I)-0S02CF3 bond in (?…”

Synthesis and characterization of anionic halogen-containing rhodacarboranes. Crystal and molecular structure of the hydrogen-bonded ion pair [HPPh3][closo-3-Ph3P-3,3-Br2-3,1,2-RhC2B9H11]

“…40%). 2 In order to conduct a more thorough study of the chemical reactivity and catalytic properties of this dimeric complex we sought a more efficient conversion of 1 to 2 employing Lewis acids (A), as shown in eq 1. (Ph3P)2(H)RhC2B9Hn + A -'/2H2 + APPh3 + [(Ph3P)RhC2B9H,,]2 (1) While the reactions of 1 with diborane and boron trifluoride did indeed proceed as per eq 1,3 that with boron tribromide produced in low yield a bromine-containing (phosphine)rhodacarborane that was shown by X-ray crystallography to be the ionic complex l, On leave from East China Institute of Textile Science and Technology, Shanghai, The Peoples Republic of China.…”

Synthesis and characterization of the difluorotris(fluorosulfate) of uranium(V): UF2(SO3F)3

“…In the case of the S03F group, several bonding types have been documented in structural as well as spectroscopic terms: (a) ionic,16•17 (b) ionic perturbed,18•19 (c) covalent monodentate,20•21 (d) bidentate bridging,22•23 (e) tridentate bridging,24 and even (f) tetradentate bridging. 25 In cases (a), (b), (e), and (0, the vibrations have generally been interpreted in terms of C3" symmetry, with 6 modes (3 A' and 3 E) including three stretching vibrations, i.e., two S-0 and one S-F, at frequencies higher than 650 cm'1. In cases (c) and (d), the symmetry is reduced to C, with the E modes becoming nondegenerate.…”