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The structure of SF(5)OSO(2)F has been investigated using gas-phase electron diffraction and quantum-chemical calculations. It is found to exist primarily in the gauche form (SF(5) group gauche relative to the S-F bond of the SO(2)F group with phi(S-O-S-F = 71(7) degrees ). A small contribution of the trans conformer cannot be excluded. Photoelectron spectroscopy gives ionization energies for the sulfur 2p electrons that reflect the relative electronegativities of fluorine and oxygen. The widths of the peaks in the photoelectron spectra indicate that there is considerable vibrational excitation associated with the core ionization of the sulfur atoms.

The first quaternary salts of pyridine (2), N-methyl imidazole (3), N-propyl triazole (4), and pyridazine (5) that contain the pentafluorosulfanyl (SF(5)) group were prepared and characterized. Neat reactions of the aromatic nitrogen compounds with SF(5)(CF(2))(n)(CH(2))(m)I (n = 2 or 4, m = 2 or 4) gave quaternary iodides 6a-c, 7a-c, 8a, and 9a,b, which were metathesized with LiN(SO(2)CF(3))(2) to form the bis(trifluoromethylsulfonyl)amides 10a-c, 11a-c, 12a, and 13a,b, in high yields. With the exception of the pyridine bis(trifluoromethylsulfonyl)amide salts, the compounds melted or exhibited a T(g) at

The reactions of bis(trifluoromethyl)sulfoxy difluoride with secondary amines give high yields of bis(trifluoromethyl)sulfoxyamines, (CF 3 ) 2 S(O)(NR 2 ) 2 where R 2 N=(CH 3 ) 2 N, (C 2 H 5 ) 2 N, NCH 2 CH 2 CH 2 CH 2 CH 2 , and CH 2 CH 2 NCH 2 CH 2 NCH 3

The crystal structure of FSO2CFHCOOH has been determined by a single-crystal X-ray study. The crystals are monoclinic, of space group P21/c, and have the following cell parameters: a = 5.0164(6) A, b = 9.658(2) A, c = 11.061(2) A, β = 90.54(1)°, Z = 4. The carboxyl groups of the molecules form the usual hydrogen-bonded, centrosymmetric dimers, but each molecule also interacts with three other neighboring molecules by hydrogen bonds from the methine hydrogen to two sulfonyl oxygens and to a carbonyl oxygen, making a four-center system. The extensive network of hydrogen bonding in this material appears to be responsible for its existence as a solid. This material has also been characterized by 1H, 13C, and 19F NMR, IR, and mass spectroscopy.

Core-ionization energies have been measured for SF(6) (S 2p), SF(5)SF(5) (S 2p), SF(5)Br (S 2p and Br 3d), and SF(5)CF(3) (S 2p and C 1s). These results, together with others that establish correlations between core-ionization energies and Pauling electronegativities, make it possible to assign group electronegativities to SF(5) and CF(3). This method gives electronegativities for these groups comparable to that of bromine, whereas analysis of the effect of these groups on acidity indicates electronegativities comparable to that of fluorine. Other methods of estimating electronegativity fall between these extremes. These disparities can be understood in part as reflecting the effects of polarizibility of the substituent, which tends to lower both the core-ionization energy and the deprotonation energy, making the electronegativity appear to be less in one case and more in the other. In addition, and possibly more important, the core-ionization energies presented here reflect the effect of the group on an adjacent atom, whereas the acidity reflects the effect on a remote atom. It appears that fluorine has a large effect on an adjacent atom but a relatively small effect on a remote atom. By contrast SF(5) and CF(3) have a relatively small effect on an adjacent atom, but this effect falls off only slowly with distance from the substituent. Thus, the effective electronegativities of CF(3) and SF(5) relative to those of the halogens depend on the site at which the molecule is probed as well as on the process that is under consideration.

Fluorinated-carbon-containing sulfonyl fluorides have received considerable attention recently, and the preparation of the completely fluorinated member of the methane series, SF{sub 5}CF{sub 2}SO{sub 2}F, and its corresponding acid, ester, and salts is reported herein. The preparations are described, and the infrared spectra measured were found to have common features with the presence of the SF{sub 5} and CF{sub 2} groups and their characteristic infrared absorption bands. Characteristic absorption bands were also noted for the SO{sub 2} and SO{sub 3}. NMR spectral data are also reported. 10 refs.

Dehydrohalogenation of the sultone F{sub 5}SCHSF{sub 2}OSO{sub 2} with the base F{sub 3}B{center dot}N(C{sub 2}H{sub 5}){sub 3} was found to yield a mixture of the ketene F{sub 5}SC(SO{sub 2})F=C=O (1) and its isomer F{sub 4}S=CCF{sub 2}OSO{sub 2} (2). Experimental conditions did not seem to alter the ratio of these compounds in the product, and the separation of 1 and 2 was found to be very difficult. It was found that treatment of the mixture with CsF resulted in the removal of 1 with recovery of 2. Treatment of the mixture of 1 and 2 with the CsF resulted in the formation of Cs{sup +}(F{sub 5}S(SO{sub 2}F)COF){sup {minus}}, which was characterized by {sup 19}F NMR spectroscopy. The reactions of 1 and 2 with HCl and HF are also reported. {sup 13}C NMR spectroscopy was also used to characterize 1. 18 refs., 1 fig.

A partir de SO 3 et de pentafluorotrifluorovinyl persulfurane, synthese du dioxyde-2,2 de pentafluorosulfuranyl-3 trifluoro-3,4,4 oxathietanne-1,2; transposition et reactions avec bases ou acides de ce compose; obtention du fluorure de l'acide fluoro fluorosulfonyl pentafluoropersulfuranyl acetique, de l'acide pentafluoropersulfuranyl methanesulfonique, de son fluorure et de ses sels de calcium ou de sodium

(C 4 H 4 N 2 H) 2 Cr 3 O 10 cristallise dans le systeme monoclinique, groupe d'espace P2 1 et sa structure est affinee jusqu'a R=0,0205

Rearrangement du dioxyde-2,2 difluoro-4,4 pentafluoropersulfuranyl-3 oxathiepanne-1,2 (A) pour conduire au compose du titre. A partir de (A) et de polyfluoroalcanols obtention de fluorosulfonyl-2 pentafluoropersulfuranyl-2 acetates d'ethyle

A new ketene F/sub 5/SC(SO/sub 2/F)=C=O has been synthesized, and it is predicted that since SF/sub 5/-containing sulfones are effective precursors to a number of derivatives potentially useful as acid electrolytes, surface-active agents, and ion-exchange resins this new ketene and its derivatives will also serve in this role. The preparation of the ketene is described in detail, and the ir and /sup 19/F NMR spectra of the SF/sub 5/-containing sulfones are discussed. 14 refs.

Synthese de l'(ethynyl pentafluoro) persulfurane a partir de (bromo-2 vinyl pentafluoro)- ou de (dibromo-1,2 vinylpentafluoro) persulfuranes

In studying molecular systems containing the pentafluorothio (SF{sub 5}) group, it was found to be necessary to synthesize SF{sub 5}CH{sub 2}CHO to serve as a precursor for pentafluorothio hydrocarbon derivatives. The vinyl ether F{sub 5}SCH = CHOCH{sub 3} was obtained from the compound F{sub 5}SCH = CHBr by treatment with methanolic sodium methoxide. The vinyl ether was then acid hydrolyzed to yield (SF{sub 5}CH{sub 2}CHO){sub 3}. Results of {sup 1}H and {sup 19}F NMR spectral studies of both the monomeric and trimeric form of the trioxane are presented. The data do not indicate isomerization in the trimer, and the crystal structure of the trimer indicated 3-fold symmetry in which the trioxane ring is situated in a chair-type conformation. 11 refs., 1 fig., 3 tabs.

Synthese de difluorofluorosulfonyl acetates de polyfluoroalkyle a partir de perfluorosultones

The purpose of the work is: (1) to determine whether water is actually needed, (2) to obtain some measure of its effect, and (3) to explain its role.