Alfred Waterfeld

New polyfluoro and perfluoroalkoxy sulfonyl fluorides. Part V. Fluorination studies

Abstract Two methods of fluorinating the ether containing disulfonyl fluoride, CH 2 (OCF 2 CF 2 SO 2 F) 2 ( 1 ) have been utilized for preparing new fluorinated derivatives. Static and electrochemical fluorination methods were effective in preparing CHF(OCF 2 CF 2 SO 2 F) ( 2 ) and CF 2 (OCF 2 CF 2 SO 2 F) 2 ( 3 ). The following new fluorinated ether salt derivatives have also been prepared and characterized: Ca[CF 2 (OCF 2 CF 2 SO 3 ) 2 ], Ca[CH 2 (OCF 2 CF 2 SO 3 ) 2 ] and Na 2 [CH 2 (OCF 2 CF 2 SO 3 ) 2 ]. Infrared, NMR and mass spectra are presented in order to support the assigned structures.

Gas-phase structures of 4,4-difluoro-1,3-dithietane-2-on, SCF2SCO, and 4,4-difluoro-1 ,3-dithietane-2-thion, SCF2SCS

Abstract The geometric structures of the two four-membered ring compounds SCF 2 SC ue5fbO and SCF 2 SC ue5fbS have been determined by gas-phase electron diffraction. The following geometric parameters (ra in A and ∠α in degrees) were obtained. SCF 2 SC ue5fbO:C(sp3)ue5f8S=1.821(12) A, C(sp2)ue5f8S=1.791 (12) A, Cue5f8F=1.343 (4)A, Cue5fbO=1.179(7) A, SC(sp3)S=97.7(13)°, SC(sp2)S=100.1(13)°, CSC=81.1(10)° and FCF=106.3(10)°. SCF 2 SC ue5fbS:C(sp3)ue5f8S=1.823(6)A,C(sp2)ue5f8S = 1.758 (6) A, Cue5f8F=1.338(4) A, Cue5fbS=1.598(5) A, SC(sp3)S=94.6(6)°, SC(sp2)S =99.2(6)°, CSC=83.1(5)° and FCF=108.1(9)°. The results are compared to the gas-phase structure of SCF 2 SC F2 and to the crystal structure of [ SCF 2 SC ue5f8F]+.

The gas-phase structure of bis (trifluorosulfur) difluoromethane CF2(SF3)2

Abstract The gas-phase structure of CF 2 (SF 3 ) 2 has been determined by electron diffraction. The experimental intensities were fitted with a model of C 2 symmetry and the following geometric parameters ( r g distances in A and ∠ α angles in degrees with 3σ error limits) were obtained: Cue5f8F=1.318 (5) A, Sue5f8F eq =1.562 (6) A, Sue5f8F ax =1.664 (4) A, Sue5f8C=1.888 (7) A, ∠SCS=108.2 (5)°, ∠FCF=109.8 (18)°, (∠CSF ax ) mean =87.1 (3)°, ∠CSF eq =97.2 (11)°, ∠F eq SF ax =88.1 (3)° and dihedral angle δ (SCSF eq )=130.8 (9)°. The two SF 3 groups are slightly tilted away from the CF 2 group resulting in a difference between the two CSF ax angles of 4.0 (10)°. The remarkably small SCS angle of 108.2 (5)° results in a very short non-bonded contact between sulfur and one axial fluorine of the opposite SF 3 group (2.66 A) which possibly indicates the presence of an Sue5f8F··S bridge.

FORMATION AND STRUCTURE OF S(O)CF2S(O)O, THE MOST SIMPLE PERFLUOROALKANE BIS(SULFINIC ACID) ANHYDRIDE

Abstract Difluoromethane bis(sulfinic acid) F 2 C(S(O)OH) 2 (3) was isolated from the hydrolysis of F 2 C(S(O)F) 2 ( 1 by moist air. Single crystals of the corresponding anhydride S(O)CF 2 S(O)O ( 2 ) were obtained after Cs′ [F 2 C(SF 3 ) 2 F] − ( 4 ) was stored in a glass vessel for several weeks. The crystal structure of 2 and preliminary results for 3 are reported.

New perfluoro-1,3-dithietane-chemistry

Abstract The BF 3 -catalysed solvolysis of SF-derivatives seems to be a general synthetic method, several other examples will be presented. Stabilities, structures, spectroscopic properties and reactivities of the compounds described will be discussed.