Gabriele Hartmann

Spectroscopic studies of trans-bis(hexafluroarsenato)tetrakis(thiazyl trifluoride)metal(II) complexes (M = Mn, Fe, Co, Ni, or Cu); crystal structure of the manganese(II) complex: an example of exceptionally short N–S bonds and of AsF6– as a unidentate ligand

The i.r. spectra of the series [M(NSF3)4(AsF6)2](M = Mn, Fe, Co, Ni, or Cu) indicate that the compounds are isostructural, with trans-AsF6 groups co-ordinated to the metal atom, and N–S bonds appreciably stronger than in free NSF3. This is confirmed by the crystal structure of trans-[Mn(NSF3)4(AsF6)2]. It crystallises in the monoclinic space group P21/n, with a= 7.496(4), b= 10.378(5), c= 13.979(6)A, β= 94.33(3)°, and Z= 2. The structure was refined to R= 0.048 for 1 226 diffractometer data. The metal ion is octahedrally co-ordinated, with Mn–Nav. 2.187, Mn–F 2.193(4), and N–Sav. 1.365 A.

Thiazyl-[bis(trifluoromethyl)nitroxide] and tris- { thiazyl-[bis(trifluoromethyl) nitroxide] }

Abstract The decomposition and trimerisation of (CF3)2 NOSN (2) are investigated, the structure determinations of 2 (by electron diffraction in the gas phase) and of [(CF3)2 NOSN]3 (6) (by x-ray crystallography) are reported.

Synthese und Struktur von [CpFe(CO)2SO2]+ AsF6- / Synthesis and Structure of [CpFe(CO)2SO2]+ AsF6–

Abstract The cationic sulfur dioxide complexes [CpFe(CO)2SO2]+AsF6- (7) and [CpCr(NO)2SO2]+AsF6- (9) are obtained in almost quantitative yield from CpFe(CO)2I(CpCr(NO)2Cl) and AgAsF6 in liquid SO2. With excess transition metal halide dinuclear halogen-bridged cations ([CpFe(CO)2IFe(CO)2Cp]+ and [CpCr(NO)2ClCr(NO)2Cp]+) are formed. The crystal structure of 7 is reported, and the bonding in the complexes is discussed in the light of spectroscopic data.

Methoden zur Darstellung kationischer Rhenium-pentacarbonyl(thiazylhalogenid)-Komplexe / Methods for the Preparation of Cationic Rhenium-pentacarbonyl(thiazylhalide) Complexes

The preparation of [Re(CO)5NSX]+AsF6- (2a X = Cl, 2b X = Br) is possible (a) by metathesis from [Re(CO)5NSF]+AsF6- with SiX4, (b) by insertion of the NS+-cation into the metal-halogenbond of Re(CO)5X and (c) by nucleophilic halide addition to the sulfur in the dicationic thionitrosyl complex [Re(CO)5NS]++.

1.3-Dichlor-5-trifluormethyl-1,3-dithia-2,4,6-triazin / 1.3-Dichloro-5-trifluoromethyl-1,3-dithia-2,4,6-triazine

The preparation of cyclo-(CF3CN)(NSCl)2 (2) from CF3CN and (NSCl)3 is reported. Dechlorination of 2 by Zn in liquid SO2 is found to yield either CF3CN3S2 or mainly CF3CN2S2, depending on the reaction conditions. The structure of 2 was determined from single crystal data.