Schwingungsspektren von Komplexen des Gold(III)-chlorids mit 2,2′- und 4,4′-Dipyridin

Vibrational Spectra of Complexes of Gold Trichloride with 2,2′-Dipyridne and 4,4′-Dipyridine, Dipyridine and 4,4′-Dipyridine By reaction of Au₂Cl₆ with 2,2′-Dipyridine and 4,4′-Dipyridine, respectively, the complexes [AuCl₂(2,2′-Dipy)][AuCl₄] (I) and [AuCl₂(4,4′-Dipy)]Cl (II) are obtained. IR and Raman spectra show that (I) has a complex chelate structure, whereas (II) is polymeric with cis-configuration of the ligands.     

Komplexe von Vanadium und Titan mit 2,2′-Dihydroxyazobenzen. Kristallstrukturen von 2,2′-Dihydroxyazobenzenato(2-)-oxo-methoxo-methanol-vanadium(V) und μ-Oxo-bis[2,2′-dihydroxyazobenzenato(2-)-oxo-vanadium(V)]

Complexes of Vanadium and Titanium with 2,2′-Dihydroxyazobenzene. Crystal Structure of 2,2′-Dihydroxybenzenato(2-)-oxo-methoxo-methanol-vanadium(V) and μ-Oxo-bis[2,2′-dihydroxyazobenzenato(2-)-oxo-vanadium(V)] By the reaction of 2,2-dihydroxyazobenzene with titanium(IV) the expected compound bis [2,2′-dihydroxybenzenato(2-)-titanium(IV)] was obtained. On the other hand in the dependence on the experimental conditions vanadium forms further compounds beside the bisligand complex. They were characterized by mass spectrometry resp. X-ray structural analysis. Crystallographic data see ?Inhaltsübersicht”?.     

Synthese und Struktur von Ruthenium(II)‐Komplexen mit Triazenido‐ und Pentaazadienido‐Liganden

Synthesis and Crystal Structure of Ruthenium(II) Complexes with Triazenido and Pentaazadienido Ligands The ruthenium(II) triazenido complex [RuCl(ClC₆H₄N₃C₆H₄Cl)(p‐cymene)] ( 1 ) is obtained by the reaction of silver bis(p‐chlorphenyl)triazenid with [RuCl₂(p‐cymene)]₂ in CH₂Cl₂, and forms air stable, orange yellow crystals. It crystallizes as 1 ·CH₂Cl₂ in the orthorhombic space group Pbca with the lattice parameters a = 3134.3(3), b = 2105.7(2), c = 769.15(4) pm and Z = 8. In the diamagnetic mononuclear complex 1 the chelating triazenido ligand coordinates with the atoms N(1) and N(3). p‐Cymene binds η⁶ with its C₆ ring. The reaction of the etherphosphane complex [RuCl₂(Ph₂PCH₂C₄H₇O₂)₂] with 1, 3‐bis(p‐tolyl)triazenid in THF yields the complex [RuCl(tolyl‐N₃‐tolyl)(Ph₂PCH₂C₄H₇O₂)₂] ( 2 ). 2 forms monoclinic, red crystals with the space group P2₁/c and a = 1521.0(2), b = 1451.8(2), c = 2073.7(2) pm, β = 99.29(1)° and Z = 4. It is air stable and diamagnetic. The triazenide ion coordinates with the atoms N(1) and N(3). One of the two etherphosphane ligands is chelating and coordinates with the P atom and one O atom, while the other ligand binds in a monodentate fashion with its P atom, resulting in a coordination number of six for the Ru^II. [Ag(tolyl‐N₅‐tolyl)]₂ reacts in THF with [RuCl₂(C₆H₆)]₂ to afford the air stable, diamagnetic pentaazadienido complex [RuCl(tolyl‐N₅‐tolyl)(C₆H₆)] ( 3 ). 3 forms monoclinic, red crystals with the space group P2₁/c and a = 1462.4(1), b = 1056.51(8), c = 1371.4(1) pm, β = 114.36(1)° and Z = 4. The chelating pentaazadienido ligand coordinates with the atoms N(1) and N(3) at the divalent Ru atom. The benzene molecule binds η⁶ with its π system.     

Synthesen und Strukturen von Übergangsmetall‐Komplexen mit Dithiophosphinato‐ und Trithiophosphonato‐Liganden

Syntheses and Structures of Transition Metal Complexes with Dithiophosphinato and Trithiophosphinato Ligands The reactions of MnCl₂ with Ph₂P(S)(SSiMe₃) produced [Mn(S₂PPh₂)₂(thf)₂] ( 1 ) and [Mn(S₂PPh₂)₂(dme)] ( 2 ) (DME = 1,2‐Dimethoxyethane). The compounds [Co₆(S₃PPh)₂(μ⁴‐S)₂(μ³‐S)₂(PPh₃)₄] ( 3 ), [Co₂(S₃PPh)₂(PPh₃)₂] ( 4 ), [Ni(S₂PPh)(PPhEt₂)₂] ( 5 ), [Ni(S₃PPh)(PPhEt₂)₂] ( 6 ) and [Cu₄(S₃PPh)₂(dppp)₂] ( 8 ) [dppp = 1,3‐Bis(diphenylphosphanyl)propane] were obtained from reactions of first‐row transition metal halides with PhP(S)(SSiMe₃)₂ in the presence of tertiary phosphines. In a reaction of PhP(S)(SSiMe₃)₂ with PhPEt₂ PhPEt₂PS₂Ph ( 7 ) was isolated. All compounds were characterized by X‐ray crystallography.     

Synthesen und Kristallstrukturen von Cu‐ und Ag‐Komplexen mit Dithiophosphinat‐ und Trithiophosphonat‐Liganden

Syntheses and Crystal Structures of Copper and Silver Complexes containing Dithiophosphinato and Trithiophosphonato Ligands The reactions of Cu^I and Ag^I salts with diphenyldithiophosphinic acid trimethylsilylester in the presence of tertiary phosphines yield the complexes [Cu(μ‐S)SPPh₂(PR₃)]₂ (R = Me 1a , ⁱPr 1b ), [Ag(μ‐S)SPPh₂(PⁿPr₃)]₂ ( 2 ), [Ag(S₂PPh₂)(PEt₃)]₂ ( 3 ), and [Cu₈(μ₈‐S)(S₂PPh₂)₆] ( 4 ). The cage complex [(PhPS₃)₂Cu₄(PMe₃)₅] ( 5 ) is obtained by the reaction of phenyltrithiophosphonic acid trimethylester. All compounds were structurally characterised by X‐ray crystallography.     

Reaktionen von Pentafulven‐Komplexen des Titans mit Nitrilen und iso‐Nitrilen — Synthese und Isomerisierungen von σ, π‐Chelatkomplexen mit Cp∼N‐Liganden

Reactions of Pentafulvene Complexes of Titanium with Nitriles and iso‐Nitriles — Synthesis and Isomerizations of σ, π‐Chelat Complexes with Cp∼N‐Ligands The reactions of fulvene complexes Cp*Ti{η⁶—C₅H₄=C(R)(R')}Cl (R = H, R' = tBu ( 1 ); R = Me, R' = iPr ( 4 )) with nitriles and iso‐nitriles, leading to σ, π‐chelat complexes with Cp∼N‐ligands, have been examined and the formed products characterized. Whereas in the reactions of 1 and 4 , respectively, with nitriles a 1, 2‐mono‐insertion of the CN‐group in the Ti—C(R)(R') (Fv) bond is observed, the reaction with iso‐nitrils leads to the insertion of two molecules iso‐nitrile. The nitrile insertion product of 1 is characterized by an imine‐enamine tautomerization. Whereas the primary built meta stable imine species ( 3 ) was only identified by NMR measurements in solution, the enamine tautomer ( 2 ) crystallized from n‐hexane, so that the crystal structure could be determined. The primary formed iminoacyl complex ( 7 ) rearranges due to the electrophilicity of the titanium centre and builds a Ti—N bond with significant N(pπ) → Ti(dπ) bonding character.     

Darstellung und Konfiguration von Tricarbonylchromat-Anionen mit SnCl3− und GeCl3− als Liganden

B₃N₃Me₆Cr(CO)₃ reacts with [AsPh₄] [SnCl₃] and [AsPh₄] [GeCl₃] in tetrahydrofuran to give [AsPh₄]₃[Cr(CO)₃(SnCl₃)₃] and [AsPh₄]₃[Cr(CO)₃(GeCl₃)₃], respectively. According to IR. and ¹³C-NMR.-data, the tricarbonylate anions possess a meridional configuration. The donor-acceptor properties of SnCl₃^? and GeCl₃^? in the anions [Cr(CO)₃(ECl₃)₃]^3? (E = Sn, Ge) are very similar. A similar synthesis of [AsPh₄]₃[Cr(CO)₃(SnF₃)₃] was not successful.     

Synthesen und Kristallstrukturen von Cu‐ und Ag‐Komplexen mit [Ta6S17]4—‐Ionen als Liganden

Syntheses and Crystal Structures of Cu and Ag Complexes with [Ta₆S₁₇]^4— Ions as Ligands In the presence of phosphines saturated solutions of the thiotantalates (NEt₄)₄[(Ta₆S₁₇)] · 3MeCN react with copper or silver salts to give new heterobimetallic Ta—M—S clusters (M = Ag, Cu). These clusters contain the intact cluster core of the [Ta₆S₁₇]^4— anion. Compounds [Cu(PMe₃)₄]₃[(Ta₆S₁₇)Cu(PMe₃)] · 2MeCN ( 1 ), (NEt₄)[(Ta₆S₁₇)Ag₃(PMe₂ⁱPr)₆] · 5MeCN ( 2 ), [(Ta₆S₁₇)Cu₄ (PMe₂ⁱPr)₈] · MeCN ( 3 ), [(Ta₆S₁₇)Cu₅Cl(PMe₂ⁱPr)₉] · MeCN ( 4 ) and [Ta₂Cu₂S₄Cl₂(PMe₂ⁱPr)₆] · 2MeCN ( 5 ) are presented herein. The structures of these compounds were elucidated by single crystal X‐ray structural analyses.     

2,2′-Diindolylmethane. VI (1). NMR-spektroskopische untersuchungen an chiralen und achiralen 2,2′-diindolylmethanen mit tryptophanester-strukturelement

The symmetric properties of some new 2,2′-diindolylmethanes with chiral centers in the sidechains were investigated on the NMR time scale. Shift experiments of the chiral 2,2′-diindolylmethanediesters 1a in the presence of 3,3,3-trifluor-2-methoxy-2-phenylpropanoic acid were discussed.