Rüdiger Mews

Coordination chemistry in and of sulfur dioxide

Abstract The review describes the syntheses of metal salts with weakly interacting anions (AlCl4u2008−, AsF6u2008−, SbF6u2008−) in the poorly coordinating solvent SO2. The metal centers in the resulting complexes might be considered as almost ‘naked’, their unusual coordination chemistry is discussed.

Molecular complexes of octafluoronaphthalene with acyclic and heterocyclic sulfur–nitrogen compounds

Abstract Mismatched molecular 1:1 complexes were prepared from C10F8 and sulfur diimides Arue5f8Nue605Sue605Nue5f8Ar 1 and Arue5f8Nue605Sue605N–SiMe3 2, 3 (1, 2: Ar=2,6–dimethylphenyl; 3: Ar=phenyl). In the case of 2, the complexation is accompanied by the unexpected cyclization of 2 into 7-methyl-2,1-benzisothiazole 4. The X-ray molecular structures of C10F8·1, C10F8·3 and C10F8 are presented; in C10F8·4 the 7-methyl-2,1-benzisothiazole 4 is highly disordered. The complexes provide very rare examples of markedly bent (C10F8·1), polyheteroatom (C10F8·3) and heterocyclic (C10F8·4) molecules involved in non-covalent arene-polyfluoroarene π-stacking interactions.

Structure and conformation of fluoroformyliminosulfur difluoride, FC(O)NSF2

Abstract The conformational properties and the geometric structure of fluoroformyliminosulfur difluoride, FC(O)Nue5fbSF 2 , were studied in the gas phase by vibrational spectroscopy and by joint analysis of gas electron diffraction (GED) intensities and rotational constants from the literature. Only one planar cis-syn conformation, with the FC(O) group cis to the SF 2 group and the Cue5fbO double bond syn to the Nue5fbS double bond, is observed. The contribution of any other conformer is estimated to be ⩽ 3%. The following skeletal geometric parameters ( r z values, estimated uncertainties are 2σ values) were derived: S ue5fb N = 1.479 (4) A , N ue5f8 C = 1.395 (6) A , S ue5f8 F = 1.586 (2) A , Cue5f8Nue5fbS = 126.7 (11)°, Nue5fbSue5f8F = 110.4 (8)°, Fue5f8Sue5f8F = 93.4 (3)°. These geometric parameters are well reproduced by HF/6-31G∗ ab initio calculations.

1 λ4,2-Thiazacyclohexa-1,4-dienes

The first [4 + 2] addition to a formal SN triple bond is found in the reaction of perfluorobutadiene with NS–F.

Three-coordinate sulphur(VI)-nitrogen species: an attempt to breathe some new life into an old topic

Abstract The review describes the syntheses, structures and reaction chemistry of three-coordinate nitrogen-containing sulphur(VI) compounds including the sulphur triimides [(RN) 3 S],

IMINO- UND BIS(IMINO)FLUORSULFINATE

Abstract By F − -addition via ‘TAS-fluoride’ (Me 2 N) 3 S + Me 3 SiF 2 - to the corresponding thionylimides and sulfurdiimides the salts RNS(O)F − (Me 2 N) 3 S + (R=CF 3 , (CF 3 ) 2 CF, SF 3 , FSO 2 ) and (RN) 2 SF − (Me 2 N) 3 S + (R=FSO 2 , (CF 3 ) 2 CF) are prepared. The new anions were unequivocally identified by their characteristic 19 F-nmr-spectra.

Arylthiazylamides: syntheses, structures, and bonding properties.

Air-sensitive, thermally unstable tris(dimethylamino)sulfonium (TAS) salts (3) of the title anions [ArNSN]- have been prepared from corresponding sulfurdiimides Ar-N=S=N-SiMe3 (2) by Si-N bond cleavage with [(Me2N)3S]-[Me3SiF2]- (TASF). They are characterized by low-temperature X-ray crystallography as Z isomers. Because of the very short terminal S-N distance (144.2 (3h)-147.9 (3i)pm) and the relatively long internal S-N distance (158.3 (3i)-160.3 (3c) pm) the [ArNSN]- ions should be regarded as thiazylamides 1b, rare species containing a S triple bond N triple bond. A bonding model is developed and the experimental results are compared with those of restricted Hartree-Fock (RHF), density functional theory (DFT), and Møller-Plesset second-order (MP2) calculations.

Synthesis and structure of {[Gd(OSO)3(µ-F2AsF4)6/2]·0.25SO2}m

Oxidation of lanthanide metals with AsF5 in liquid SO2 yields the corresponding polymeric {[M(SO2)n](AsF6)3}m(1a–j, M = Y, La, Ce, Pr, Nd, Sm, Gd, Dy, Er, Yb) where the metal centres are bridged by AsF6 units; the X-ray crystal structure of the Gd complex 1g is reported.

P3N3F5NPF2NPF2NPF52–: a Cyclophosphazene with a phosphazene side-chain dianion by F–-induced ring-opening of P3N3F6

[(Me2N)3S+]2[P3N3F5NPF2NPF2NPF5]2– is prepared from the reaction of (Me2N)3S+Me3SiF2–and P3N3F6 and its X-ray crystal structure determined.

Alkylation of OPF3 by MeOSO+AsF−6: the unexpected formation of a dioxadiarsetane☆

Abstract Attempts to alkylate OPF3 with CH3OSO+AsF−6 unexpectedly led to the formation of (CH3OAsF4)2 (1) a four-membered A2O2 heterocycle. 1 decomposes slowly to give (CH3)3O+AsF−6 (2) and {(OAsF3)n}. The adduct F5Sb·OPF3 (4) was isolated from OPF3 and CH3OSO+SbF−6. OPF2NMe2 and CH3OSO+AsF−6 also yielded the corresponding adduct F2(Me2N)PO·AsF5 (5). Reaction mechanisms are discussed, the structures of 1, 2 and 4 are reported.