R. Mews

Heterospin π-Heterocyclic Radical-Anion Salt: Synthesis, Structure, and Magnetic Properties of Decamethylchromocenium [1,2,5]Thiadiazolo[3,4-c][1,2,5]thiadiazolidyl

Decamethylchromocene, Cr(II)(eta(5)-C(5)(CH(3))(5))(2) (2), readily reduced [1,2,5]thiadiazolo[3,4-c][1,2,5]thiadiazole (1) in a tetrahydrofuran solvent at ambient temperature with the formation of radical-anion salt [2](+)[1](-) (3) isolated in 97% yield. The heterospin salt 3 ([2](+), S = 3/2; [1](-), S = 1/2) was characterized by single-crystal X-ray diffraction as well as magnetic susceptibility measurements in the temperature range 2-300 K. The experimental data together with theoretical analysis of the salts magnetic structure within the CASSCF and spin-unrestricted broken-symmetry (BS) density functional theory (DFT) approaches revealed antiferromagnetic (AF) interactions in the crystalline 3: significant between anions [1](-), weak between cations [2](+), and very weak between [1](-) and [2](+). Experimental temperature dependences of the magnetic susceptibility and the effective magnetic moment of 3 were very well reproduced in the assumption of the AF-coupled [1](-)...[1](-) (J(1) = -40 +/- 9 cm(-1)) and [2](+)...[2](+) (J(2) = -0.58 +/- 0.03 cm(-1)) pairs. The experimental J(1) value is in reasonable agreement with the value calculated using BS UB3LYP/6-31+G(d) (-61 cm(-1)) and CASSCF(10,10)/6-31+G(d) (-15.3 cm(-1)) approaches. The experimental J(2) value is also in agreement with that calculated using the BS DFT approach (-0.33 cm(-1)).

The oxidation of perhaloalkyl-sulphurdifluoride-imides by oxygen difluoride

Abstract Perhaloalkyl Sulphuroxidifluoride imides R NSOF 2 (R = CF 3 -, C 2 F 5 -, i-C 3 F 7 -, CF 2 Cl-, CF 2 Br-CF 2 -) are isolated in high yield from the photochemical reaction of OF 2 with the appropriate difluoride-imides. In all these reactions the difluoride-diimides RNSF 2 NR are found as by-products.

Transition metal sulfur dioxide hexafluoroarsenates and hexafluoroantimonates

Abstract The preparation and characterization by X-ray crystallography of transition metal sulfur dioxide hexafluoroarsenates of the general formula [M(SO2)x](AsF6)2 1 (1a: M=Mn, x=2; 1c: M=Co, x=4; 1e: M=Cu, x=4) and the hexafluoroantimonate [Co(SO2)2](SbF6)2 3 is reported. The structural features of the compounds mentioned are compared with those of [Fe(SO2)4](AsF6)2 (1b) and [Ni(SO2)6](AsF6)2 (1d), reported previously. The structural diversity of transition metal sulfur dioxide complexes is discussed.

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.

The structure of dimethylamino-sulfurtrifluoride and some aspects of amino-sulfur (IV)-fluorine chemistry

Abstract The structure of Me 2 NSF 3 - determined by electron diffraction - is reported and the mechanism of its reaction with SO 2 is discussed.

The first N-alkyl-N′-polyfluorohetaryl sulfur diimide

Abstract The first AlkNSNHetF sulfur diimide 6 (Alk=adamant-1-yl, HetF=2,3,5,6-tetrafluoropyrid-4-yl) was prepared by trapping of the corresponding alkylthiazylamide [AlkNSN]− 3 with pentafluoropyridine, followed by X-ray structural characterization. For 6, the Z,E configuration was found. From the reaction of 3 with octafluoronaphthalene, hexafluorinated naphthothiadiazole 7 was isolated along with the parent AlkNH2.

N-Difluorphosphoryl-N',N″-bis(t-butyl)-Schwefeltriimid

Abstract (t-BuN=) 2 S=NPOF 2 ( 5 ) is prepared in 55 % yield from and OPF 2 NCO. In moist ether water is added to 5 forming (t-Bu-N-) 2 S(O)NPOF 2 (6) almost quantitatively.

A new SF5-containing solid ether-bis(β-pentafluorothio-β-fluorosulfonyl-ethyl)ether

Abstract The reaction of pentafluorothio(fluorosulfonyl)ketene with formaldehyde has yielded the novel solid ether [SF 5 CH(SO 2 F)CH 2 ] 2 O, 1 . The crystal structure has been determined: crystal class tetragonal I4; a = b = 11.069(2) A, c = 6.0780(1) A; α=β=γ=90°; V = 744.7(2) A 3 ; Z = 2. Hydrogen bonding (CH⋯O) is believed responsible for the solid state nature of this material.

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.

CCDC 805247: Experimental Crystal Structure Determination

Related Article: E.A.Suturina, N.A.Semenov, A.V.Lonchakov, I.Yu.Bagryanskaya, Y.V.Gatilov, I.G.Irtegova, N.V.Vasilieva, E.Lork, R.Mews, N.P.Gritsan, A.V.Zibarev|2011|J.Phys.Chem.A|115|4851|doi:10.1021/jp2019523