Übergangsmetallkomplexe von Diazenen, XXIV [1]. Komplexierung und N=N-Spaltung von Diazenen durch Dicarbonylbis(cyclopentadienyl)titan / Transition Metal Complexes of Diazenes, XXIV [1] Complexation and N = N-Cleavage of Diazenes by Dicarbonylbis(cyclopentadienyl)titanium (original) (raw)
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Zeitschrift für Naturforschung B, 1994
Syntheses and structures of homoleptic 1,4-diaza-1,3-diene (DAD) complexes of titanium are described. The spiranoid DAD complexes of formula (DAD)2Ti 3a-c are formed by reaction of TiCl4·2THF with the disodium salts Na2DAD 2a-c or by reduction of TiCl4·2TH F with magnesium in presence of two equivalents of DAD 1a-c . The endiaide complexes 3a-c are thermally stable, very sensitive to oxygen and water, and soluble in all com monorganic solvents. An X-ray crystal structure determination of 3 c reveals the titanium atom to be in a strongly distorted tetrahedral environment. The two five-membered metallacyclic rings are folded along the N,N′ axis. Temperature-dependent 1H NMR spectra of 3a-c indicate a rapid intramolecular inversion of this non-planar ring system in solution even at room temperature. Reduction of TiCl4·2THF with magnesium in presence of excess DAD 1d-f leads to the formation of the blue-violet complexes (DAD)3Ti 4d-f. At low temperatures three sterically crowded DAD lig...
Zeitschrift für Naturforschung B, 1986
Zeitschrift für Naturforschung B, 1988
Slow reaction of TiCl4 with S4N4 in CH2Cl2/CCl4 produces a mixture of two crystalline dinuclear complexes of composition [TiCl4(S4N4)]2. Crystal data for the orange-yellow α-isomer: monoclinic, space group P21/n with a = 11.608(3) Å. b = 8.304(3) Å, c = 10.938(5) Å, β = 101.06(4)° and Z = 2. Crystal data for the red-brown β-isomer: monoclinic, space group P21/c with a = 11.220(2) Å, b = 13.868(2) Å, c = 14.839(4) Å, β = 106.18(2)° and Z = 4. Crystal structure analyses reveal that the S4N4 molecules in the α-form act as 1,3-N,N′-bonded bridging ligands and in the β-form as N-bonded monodentate ligands.
Chemische Berichte, 1991
Ironcarbonyl complexes / ortho-Metallation 1 o-Semidine rearrangement Iron Carbonyl Induced o-Semidine Rearrangement of 1-Alkyl-2-aryldiazenes Irradiation of pentacarbonyl iron in the presence of NFE!(CO)~-Fe(C0)3N(H)RC6H3 (1 a-c). The structure of 1 a Me3CPN=N-Ar (Ar = PhenYl, P-tolYl~ p-CH30C6H4) Pro-has been elucidated by X-ray structure analysis, Dynamic 13Cduces in the first Step ortho-metallated COmpleXeS Of the type NMR spectra indicate restricted rotation of the Me3C group Me3C-N-N(H)RC6H3Fe(C0)3Fe(C0)3 (2ac, R = H, Me, and hindered carbonyl scrambling for the latter and former MeO). In a thermal consecutive step these intermediates comP1exes~ undergo an o-semidine rearrangement to Me3C-Umsetzungen von 1,2-Diaryldiazenen mit Eisencarbonylen verlaufen abhangig von der Natur der Arylgruppen und den Reaktionsbedingungen. Im allgemeinen entstehen zweikernige Hexacarbonylkomplexe A (R = H, OCH3), die ein o-Semidin (0-Aminodipheny1amin)-Geriist besitzen2'.
Chemische Berichte, 1992
Transition Metal Complexes of Diazenes, XXX[1]. – On the Photoreaction of Octacarbonyl Dimetallaheterocycles with Bis(phosphanes)*Irradiation of (CO)4Cr(μ‐pmd)2Cr(CO)4 (1) (pmd = 3,3‐penta‐methylenediazirine) in the presence of bis(dimethylphosphanyl)methane (dppm) affords (CO)3(μ‐pmd)2(μ‐dppm)Cr(CO)3 (2b) and (CO)4Cr(μ‐pmd)(μ‐dppm)Cr(CO)4 (3b) which both contain boat‐like dimetallaheterocyclic rings as indicated by X‐ray analysis. Contrary to that, in the presence of cis‐1,2‐bis(diphenylphosphanyl)ethene the reaction affords the known Cr(CO)4(cdpe) (4c) by complete cleavage of the dimetalla‐heterocycle.
Zeitschrift für Naturforschung B, 1992
The crystal structure of (AsPh4)2[Te(S2C = C(CN)2)2] has been determined by X-ray diffrac tion and the electronic structure has been calculated using an effective core potential approach for core electrons of Te and minimal basis-sets for valence electrons of Te and electrons of S, C and N. Te is situated in the center of planar [Te(S2C = C(CN)2)2]2- anions and is coordinated by four sulfur atoms in a trapezoid geometry with Te -S distances of 2.463(4), 2.524(4), 2.819(4) and 2.945(3) Å. The compound crystallizes in the triclinic space group P 1̄ with a = 9.562(5), b = 11.430(6), c = 27.319(20) Å, α = 93.248(2), β = 91.06(2), γ = 112.23(4)° and Z = 2. The trapezoid geometry allows a straightforeward mixing of Te 5 s-and one 5p-orbital giving rise to the formation of sp-hybride orbitals.