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1Author    BernhardG. Ollasa, S. Bernd, Peiser1, H. Artm, Ut Stahp, Jürgen Sieglenb, Joachim StrählebRequires cookie*
 Title    Electrochemistry of Oxygenation Catalysts, Part 6* Electrosynthesis, Structure, Analytical and Electrochemical Properties of Monomeric [Coin(salen)(DMF)2]+ X' Salts (X = PF6, C104)  
 Abstract    Electrochemistry [CoH1(salen)(DMF)2]+ X" salts [X = PF6, C104; salen = bis(salicyliden)ethylendiiminato; DMF = dimethylformamide] have been synthesized by electrochemical and chemical (air) oxidation of Co"(salen). Their monomeric structure with two DMF molecules in the axial positions in both the solid state and DMF solution is shown by X-ray crystal structure analysis, thermal analysis, mass spectroscopy, and 'H and l3C NMR spectroscopy. The electrochemical reduction of the [Coni(salen)(DMF)2]+ cation is investigated by cyclic voltammetry and com­ pared to the oxidation of the neutral CoH(salen). The redox reaction connecting the cobalt(II) and the cobalt(III) species appears to be a quasi-reversible electron transfer. These properties make the [Co1 1 (salen)(DMF)2]+ X-salts starting materials for the analysis of the interaction of basic substrates with cobalt(III) species in the context of the biomimetic oxygenation reactions catalyzed by such complexes. 
  Reference    Z. Naturforsch. 51b, 388—398 (1996); received September 4. 1995 
  Published    1996 
  Keywords    Cobalt Complexes, Oxygenation Catalysts, Crystal Structure, Solution Structure 
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 TEI-XML for    default:Reihe_B/51/ZNB-1996-51b-0388.pdf 
 Identifier    ZNB-1996-51b-0388 
 Volume    51 
2Author    Berthold Kersting, Gabriel SiedleRequires cookie*
 Title    Reactivity of Cobalt(III) Amine-Thiolate Complexes with Terminal and Bridging Thiolate Functions towards Hydrogen Peroxide  
 Abstract    The reactivity of Co111 amine-thiolate complexes with terminal and bridging thiolate func­ tions towards oxidizing agents has been investigated. The mononuclear Co N3S3 complex [Coni(L1)] (2) (H3L 1 represents the hexadentate ligand /V,jV',./V"-Tris(2-thio-benzyl)-1,1,1 -tris-(aminomethyl)ethane) featuring three terminal thiolate ligands, and the binuclear N3Com-(Ai-S)3ComN3 complex [Coni2(L2)]3+ (4) (H3L2 = N, A^/V''-Tris-[2-thio-3-aminomethyl-5-terr-butyl-benzyl]-l,l,l-tris(aminomethyl)ethane) featuring three bridging thiolates were selected. Hydrogen peroxide was the oxidizing agent. Whereas the thiolato-bridged complex 4 is resis­ tant towards oxidation by hydrogen peroxide, 2 undergoes a ligand-based oxidation reaction to give the amine-sulfinate complex [Co(L'')] 5, where all three terminal thiolates have been oxidized to sulfinates without gross structural changes of the parent complex 2. In contrast to 4, the cyclic voltammogram of 2 reveals an irreversible oxidation wave at E = +0.52 V vs SCE which can be attributed to a ligand-centered oxidation reaction. 4 and 5 have been structurally characterized by X-ray crystallography. 
  Reference    Z. Naturforsch. 55b, 1179—1187 (2000); received August 17 2000 
  Published    2000 
  Keywords    Cobalt Complexes, Amine-Thiolate Ligands, Sulfinate Complexes 
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 TEI-XML for    default:Reihe_B/55/ZNB-2000-55b-1179.pdf 
 Identifier    ZNB-2000-55b-1179 
 Volume    55 
3Author    JaapN. Louwen, RonaldR. Andréa, DerkJ. Stufkens, Ad OskamRequires cookie*
 Title    He(I) and He(II) Photoelectron Spectra of Some L3MCo(CO)4 Complexes (M = Si, Ge, Sn, Pb and L = Cl, Br and CH3)  
 Abstract    The He(I) and He(II) photoelectron spectra of L3MCo(CO)4 complexes (M = Si, Ge, Sn, and Pb and L = Cl, Brand CH3) are reported. Bands attributable to the metal-cobalt bond, cobalt 3d and CO orbitals are assigned in agreement with a qualitative MO model. Rela-tivistic effects and He(I)/He(II) intensity ratios prove to be important in assigning these ultraviolet photoelectron spectra. 
  Reference    Z. Naturforsch. 38b, 194—202 (1983); received October 3 1982 
  Published    1983 
  Keywords    Metal-Metal Bond, UPS, Cobalt Complexes, Relativistic Effects, Ionization Potentials 
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 TEI-XML for    default:Reihe_B/38/ZNB-1983-38b-0194.pdf 
 Identifier    ZNB-1983-38b-0194 
 Volume    38 
4Author    A. Asam, B. Janssen, G. Hüttner, L. Zsolnai, O. W. AlterRequires cookie*
 Title    tripod-Eisen-und rri/?o*/-Cobalt-Komplexe mit Acetonitril als Stützliganden {tripod = RCH2C(CH2PPh2)3; R = H, Ph) tripod-Iron and m pod-Cobalt-Complexes with Acetonitrile as Supporting Ligands (tripod = RCH2C(CH2PPh2)3; R = H, Ph)  
 Abstract    The tripod ligands R C H ,C (C H 2 PPh2) 3 react with (C H 3 CN)6Fe(BF4) 2 to yield the 
  Reference    Z. Naturforsch. 48b, 1707—1714 (1993); eingegangen am 29. Juli 1993 
  Published    1993 
  Keywords    T ripod Ligands, Iron Complexes, Cobalt Complexes, Synthesis, Structure 
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 TEI-XML for    default:Reihe_B/48/ZNB-1993-48b-1707.pdf 
 Identifier    ZNB-1993-48b-1707 
 Volume    48 
5Author    Z. NaturforschRequires cookie*
 Title    Chemie polyfunktioneller Moleküle, 114 [1]  
 Abstract    Synthese und Struktur eines ionischen und nichtionischen, cyclischen Carbaphosphazens und eines Cobalt(III)phosphazen-Komplexes C hem istry of Polyfunctional M olecules, 114 [1] Synthesis and Structure of an Ionic and N on Ionic Cyclic C arbaphosphazene and of a C o b alt(III)phosphazene Com plex Jochen E llerm ann3 *, Jörg S u tter3, Falk A. K noch3, M atthias M oll3, W alter B au e rb Reaction of Ph2 P -N -P (P h 2) -N -(Ph2)PCoP(Ph2) -N -P (P h 2) -N -PPh2 (1) in CH2 C12 with benzimidazole yields (CH2 -PPh2 = N -PPh2 = N -PPh2)+C l" ([4]+C L). The salt [4]+BPh4" has been prepared in THF by metathesis of [4]+C l_ with N aBPh4. D eprotonation of the cationic ring in [4]+BPh4_ was accomplished using l,8-diazabicyclo[5.4.01 7 ]undec-7-ene and resulted in the six-membered carbacyclophosphazene CH=PPh2 -N = P P h 2 -N = P P h 2 (6). Treating 1 with 8 -hydroxyquinoline in CH2 C12 yields the octahedral c/s-complex (N 0) 2 CoP(Ph2) -N -P (P h 2) -N -P P h 2 (7) (N O = 8 -oxyquinolinate group). The com ­ pounds [4]+BPh4~, 6 and 7 are characterized by their IR, Raman, 3 1 P{1H) NM R, 1 3 C{1 H} N M R , !H NMR and mass spectra. Crystals suitable for X-ray structure analyses have been obtained for [4]+BPh4_ and_7x0.5 CH2 C12. The colourless plates of [4]+BPh4_ crystallize in the triclinic space group P I, with the lattice constants a = 1172.7(3), b = 1326.2(3), c = 1806.1(6) pm; a = 100.79(2), ß = 103.71(3), y = 108.18(2)°. The black blocks o f 7 x 0 .5 C H 2 C12 crystallize in the monoclinic space group P 2 x!c with the lattice constants a = 1159.0(10), b = 2008.9(10), c = 2034.6(12) pm; ß = 105.86(5)°. 
  Reference    Z. Naturforsch. 49b, 1763—1773 (1994); eingegangen am 25. April 1994 
  Published    1994 
  Keywords    Cyclic Carbaphosphazene Systems, Cobalt Complexes, Syntheses, NM R Spectra, X-Ray 
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 TEI-XML for    default:Reihe_B/49/ZNB-1994-49b-1763.pdf 
 Identifier    ZNB-1994-49b-1763 
 Volume    49