Wolfgang Bühlmeyer

Dicarbonyl(cyclopentadienyl)mangan-komplexe mit phosphino- und arsino-substituierten schwefeldiimiden als brückenliganden. Kristallstruktur und stereochemie von S{NPtBu2[Mn(CO)2Cp]}2☆

Abstract The phosphino/arsino-substituted sulphur diimides tBu2E′NSNEtBu2 (E = E′ = P (1); E′ = P, E = As (2) and E = E′ = As (3)) add two coordinatively unsaturated complex fragments [CpMn(CO)2] to give binuclear coordination compounds (4–6) which contain the intact sulphur diimide as a bridging ligand 1 . According to the X-ray structure analysis of S{NPtBu2[Mn(CO)2Cp]}2 (4) (and of the isomorphous arsino compound S{NAstBu2[Mn(CO)2Cp]}2 (6)), the crystalline sulphur diimide possesses the cis,trans-configuration. However, the angle at the nitrogen atom of the cis-configured SN double bond in 4 is considerably enlarged (151.3(1)°) as compared to that of the trans-SN double bond (119.8(2)°). The enlarged angle, caused by the very large PtBu2[Mn(CO)2Cp} substituent, gives rise to a significant shortening of both the SN and NP distances on the side of the cis-configurated SN double bond. The angle at the central sulphur atom is found to be 118.4(2)°. The 1H, 13C and 31P NMR spectra of the new complexes 4–6 indicate that the cis/trans configuration of the sulphur diimide skeleton also predominates in solution.

Umsetzungen von schwefeldiimiden mit dreikernigen osmiumclustern: Synthese, festkörperstruktur und dynamische eigenschaften von (μ-H)Os3(CO)10]μ-N(H)SN(SiMe3)2]

Abstract The reaction of bis(trimethylsilyl) sulphur diimide, S(NSiMe 3 ) 2 , with H 2 Os 3 (CO) 10 results in the formal addition product (μ-H)Os 3 (CO) 10 [μ-N(H)SN(SiMe 3 ) 2 ] (II). In the solid state, II contains a closed Os 3 triangle, the shortest edge of which is bridged by both a μ-hydride and a μ 2 -N(H)SN(SiMe 3 ) 2 ligand. The intact NSN backbone is oriented perpendicular to the Os 3 plane. The only fluxional process observed by variable-temperature 13 C NMR spectroscopy in solution involves pseudo-rotation of the unbridged Os(CO) 4 unit.

Die reaction von bis(trimethylsilyl)schwefeldiimid mit dodekacarbonyl-triruthenium, röntgenstrukturanalyse des produkts Ru2(CO)4[μ-Me3Si-NSN-COSiMe3]2

Abstract An unusual binuclear complex, Ru2(CO)4[μ-Me3Si-NSN-COSiMe3]2, is formed when bis(trimethylsilyl) sulfur diimide, S(NSiMe3)2, reacts with Ru3(CO)12 in boiling hexane. The X-ray structure analysis reveals a centrosymmetric molecule containing two [Ru(CO)2] units which are incorporated into a pentacyclic system with a ten-membered ring as largest perimeter. This ring possesses a chair conformation, it contains two transannular Ru-N bonds and, on the perimeter, two RuNS triangles. Apparently a ruthenium-coordinated CO ligand is inserted into a N-SiMe3 bond of S(NSiMe3)2; a carbene-type ligand is thus formed, which is both a chelating and a bridging ligand. The coordinated SN bond of the original sulfur diimide is lenghtened to 1.721(3) A.

Schwefeldiimid, S(NH)2, und monosubstituierte Schwefeldiimide, S(NR)(NH), mit R = tert-Butyl und Trimethylsilyl / Sulfur Diimide, S(NH)2, and Monosubstituted Sulfur Diimides, S(NR)(NH), with R = tert-Butyl and Trimethylsilyl

The unstable parent compound of the sulfur diimides, S(NH)2 (1), has been obtained in solution by stoichiometric protonation of the anion SN22- in K2SN2 with acetic acid. An analogous protonation of the salts S(NR)(NK) leads to the m onosubstituted sulfur diimides S(NR)(NH) containing bulky substituents such as R = tert-butyl (2) and R = trimethylsilyl (3); 2 and 3 can be isolated as white solids below -40 °C. The temperature-dependent 1H NMR spectra of 1-3 indicate the presence of two isomers in solution (ratio 4:1) which are reversible interconverted.

Ru2(CO)6(ButNS) − Ein tert-Butylschwefelimid-Komplex mit Ru2NS-Tetrahedrangerüst / Ru2(CO)6(BUtNS) - A tert-Butyl Sulfur Imide Complex Containing a Ru2NS Tetrahedrane Skeleton

Abstract Fragmentation of bis(rm-butyl) sulfur diimide, S(NBut)2 (1a), in the presence of Ru3(CO)12 leads to a yellow tetrahedrane-type complex Ru2(CO)6(ButNS) (3a) containing tert-butyl sulfur imide as a six-electron ligand. According to the X-ray structure determination the N−S bond (1.716 Å) is arranged perpendicular to the Ru−Ru axis (2.661 Å).