Recent advances in the staudinger reaction

Influencing the Aggregation of Manganese Complexes by Different Bases: Formation of [Mn(O2CCF3)2(py)4] and [Mn3(O2CCF3)6(benz)6]



Manganese powder reacts quantitatively with trifluoroacetic acid to yield Mn(O2CCF3)2 (1). The aggregation of 1 is directed by different N-containing bases. Pyridine (py) forms the mono-nuclear complex [Mn(O2CCF3)2(py)4] (2), while benzonitrile (benz) yields the trinuclear complex [Mn3(O2CCF3)6(benz)6] (3). The X-ray structures of 2 and 3 are described.

Steuerung der Aggregation von Mangankomplexen durch unterschiedliche Basen an den Beispielen [Mn(O2CCF3)2(py)4] und [Mn3(O2CCF3)6(benz)6]

The nine transition metal hexafluorides present a unique series of closely related compounds. Deviations from octahedral structures are influenced by Jahn–Teller effects and spin orbit coupling. The most pronounced chemical behaviour is the increasing electron affinity in the direction WF6→ PtF6 and MoF6→ RuF6, so that with PtF6 and RuF6 values of 7 eV or higher are reached. All hexafluorides can be used as one electron oxidants, starting with mild (WF6) up to extreme (PtF6, RuF6) oxidation power.

The transition metal hexafluorides

Formation and O-atom reactivity of the Os(IV)-sulfilimido and Os(IV)-sulfoximido complexes, cis-/trans-[Os(IV)(tpy)(Cl)(2)(NSC(6)H(3)Me(2)] and cis-/trans-[Os(IV)(tpy)(Cl)(2)(NS(O)C(6)H(3)ME(2))].

The reaction of Cp2*UCl2 with HNSPh2 produces Cp2*UCl2(HNSPh2), which is the first structurally characterized complex of a sulfilimine. The hydrolysis of Cp2*UCl2(HNSPh2) with HNSPh2 · H2O yields a tetrauranium cluster whose heavy atom structure has been determined by x-ray diffraction and which is formulated as a UIV/UV complex: [Cp*(Cl)(HNSPh2)U(μ3-O)(μ2-O)2U(Cl)(HNSPh2)2]2.



Uran-Sulfilimin-Chemie Darstellung von Cp2*UCl2(HNSPh2) und dessen Hydrolyse mit HNSPh2 · H2O



Die Reaktion von Cp2*UCl2 mit HNSPh2 ergibt Cp2*UCl2(HNSPh2), das den ersten strukturell charakterisierten Komplex eines Sulfilimins darstellt. Die Hydrolyse von Cp2*UCl2(HNSPh2) mit HNSPh2 · H2O ergibt einen Tetrauran-Cluster, dessen Schweratomstruktur rontgenographisch bestimmt wurde und der als UIV/UV-Komplex [Cp*(Cl)(HNSPh2)U(μ3-O)(μ2-O)2U(Cl)(HNSPh2)2]2 formuliert wird.

Uranium‐sulfilimine chemistry. The preparation of Cp2*UCl2(HNSPh2) and its hydrolysis with HNSPh2 · H2O

Aus Ph2SNH wird mit Me3SiNMe2 durch Metathese S,S-Diphenyl-N-(trimethylsilyl)sulfimin (1) erhalten. WF6 reagiert mit 1 im Molverhaltnis 1:1 zu F5WNSPh2 (2) und im Molverhaltnis 1:2 zu F4W(NSPh2)2 (3). Von 3 wird eine Rontgenstrukturanalyse vorgelegt.



Preparation of S, S-Diphenyl-N-(trimethylsilyl)sulfimine and Reactions with Tungsten Hexafluoride - X-Ray Structure Analysis of F4W(NSPh2)



Ph2SNH reacts with Me3SiNMe2 to give S,S-diphenyl-N-(trimethylsilyl)sulfimine (1) in a metathesis. Reaction of WF6 with 1 in a 1:1 molar ratio leads to F5WNSPh2 (2); a 1:2 molar ratio results in the formation of F4W(NSPh2)2 (3). The structure of 3 is confirmed by an X-ray analysis.

Darstellung von S,S-Diphenyl-N-(trimethylsilyl)sulfimin und Reaktionen mit Wolframhexafluorid – Einkristall-Röntgenstrukturanalyse von F4W(NSPh2)2

Heterocycles Containing Tungsten, Phosphorus, Sulphur, and Nitrogen in the Ring Skeleton



The new ligand Me2S(NPPh2NSiMe3)2 (2), prepared from Me2S-(NPPh2)2 (1) and Me3SiN3, reacts with WF6 and WCl6 to form the heterocycles Me2S(NPPh2N)2WF4 (3a) and Me2S(NPPh2N)2WCl4 (3b). The X-ray single-crystal structure analysis exhibits a puckered eight-membered ring with alternating short and long bond lengths. 3a crystallizes with one molecule of dimethylformamide in the space group Cc with a = 1247.3(6), b = 1728.5(9), c = 1543.1(8) pm and β = 102.41(3)°.

Wolframheterocyclen mit Phosphor, Schwefel und Stickstoff als Ringbausteine

Abstract S,S-Diphenyl-N-(trimethylsilyl)sulfimine (1) reacts in a molar ratio of 1:1 with V(O)Cl3 , V(O)F3 , NbCl5, MoCl5 and FeCl3 to yield Ph2S=NV(O)Cl2 (2). Ph2S=NV(O)F2 (3). Ph2S=NNbCl4 · CH3CN (4), Ph2S=NMoCl4·CH3CN (5). and (Ph2S=NFeCl2)2 (6), respectively. The crystal structures of 2 and (dimeric) 6 are reported.

Neue Übergangsmetallkomplexe mit dem Ph2S=N-Liganden / New Transition Metal Complexes with the Ligand Ph2S=N

Abstract Me2SN2P2Ph4M(CO)4 complexes (1) (M: 1 a Cr, 1 b Mo, 1 c W) have been synthesized from Me2S(NPPh2)2 and C7H8M(CO)4 . 1a-1c are stable at room temperature, 1 b crystallizes in the space group P21212 with cell constants a = 2486.3(2); b = 1488.8(1); c = 882.0(1) pm.

N,N′-Bis(diphenyIphosphino)-S,S-dimethylsulfodiimin – ein Ligand für cyclische Übergangsmetallkomplexe/ N,N′-Bis(diphenylphosphino)-S,S-dimethylsulfodiimine – a Ligand for Cyclic Transition Metal Complexes

Michael Zimmer

Papers

Darstellung von S,S-Diphenyl-N-(trimethylsilyl)sulfimin und Reaktionen mit Wolframhexafluorid – Einkristall-Röntgenstrukturanalyse von F4W(NSPh2)2

Wolframheterocyclen mit Phosphor, Schwefel und Stickstoff als Ringbausteine

Neue Übergangsmetallkomplexe mit dem Ph2S=N-Liganden / New Transition Metal Complexes with the Ligand Ph2S=N

N,N′-Bis(diphenyIphosphino)-S,S-dimethylsulfodiimin – ein Ligand für cyclische Übergangsmetallkomplexe/ N,N′-Bis(diphenylphosphino)-S,S-dimethylsulfodiimine – a Ligand for Cyclic Transition Metal Complexes