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1Author    Arnd Vogler, Alfred KernRequires cookie*
 Title    Photoredox Reaction of Jrans-4-Stilbenecarboxylatopentaamminecobalt(III)  
 Abstract    The irradiation (A = 313nm) of aqueous [Co(III)(NH3)5TSC] 2 + (TSC -= transA-stilbenecarboxylate) leads to a redox reaction with formation of Co 2+ as has been shown previously. The TSC -ligand is oxidized to the radical in the primary photoreaction. At higher complex concentrations IO -2 M) this TSC radical is oxidized to stable products (0 = 0.09 ± 0.02) by [Co(NH3)5TSC] 2 +, which is reduced to Co 2 + leading to release of the TSC" ligand (0 = 0.07 ± 0.02). Co 2 + is thus formed by both the secondary and the primary photochemical reaction (ÖWraii = 0.16). At low complex concentrations (< 10 -4 M) in the presence of air, the primary TSC radical is scavenged by O2. Benz-aldehyde is an oxidation product. This reduces the formation of Co 2 + to 0 = 0.09 ± 0.02, which is taken to be the efficiency of the primary photochemical step. It is suggested that the photoredox reaction is initiated by an electron transfer from the first excited singlet of the TSC -ligand. As shown by sensitization experiments, the population of the lowest TSC -triplet leads to the usual trans/cis isomerization of the TSC -ligand, but not to the redox reaction. 
  Reference    Z. Naturforsch. 34b, 271—274 (1979); received November 13 1978 
  Published    1979 
  Keywords    Redox Reaction, Photochemistry, Cobalt(III) Complex, Stilbenecarboxylate 
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 TEI-XML for    default:Reihe_B/34/ZNB-1979-34b-0271.pdf 
 Identifier    ZNB-1979-34b-0271 
 Volume    34 
2Author    Wolf-H GündelRequires cookie*
 Title    Untersuchungen an quartären Pyridinium-Salzen, XV [1] Pseudobasen und Redoxprodukte bei der Umsetzung von Pyridinium-Salzen mit Alkoholat Investigations of Quaternary Pyridinium Salts, XV [1] Pseudobases and Redox Products in the Reaction of Pyridinium Salts with Alcoxides  
 Abstract    Mono-and diquaternary pyridinium salts substituted in 3-position with electron with-drawing groups, react with alcohols under basic conditions to give 6-alcoxy-l,6-dihydro-pyridines. Symmetric dipyridinium salts react in aqueous alkaline solution to products with 6-pyridone and dihydropyridine moiety. This redox reaction depends on the length of the bridge connecting the pyridinium rings. Pyridinium salts can be reduced by aluminiumtriisopropoxide to 1,4-dihydropyridines. 
  Reference    Z. Naturforsch. 38b, 873—883 (1983); eingegangen am 21. Februar 1983 
  Published    1983 
  Keywords    Pyridinium Salts, Insertion Reaction, Redox Reaction 
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 TEI-XML for    default:Reihe_B/38/ZNB-1983-38b-0873.pdf 
 Identifier    ZNB-1983-38b-0873 
 Volume    38 
3Author    AngelikaAnna Meyer, Wolfgang Hartl, MalischRequires cookie*
 Title    Übergangsmetall-substituierte Phosphane, Arsane und Stibane, XXX [1] Redoxreaktionen zwischen Triorganodibromphosphoranen oder -arsoranen und Ubergangsmetall -Anionen Transition-Metal Substituted Phosphanes, Arsanes and Stibanes, XXX [1] Redox Reactions between Triorganodibromophosphoranes or -arsoranes and Transition Metal Anions  
 Abstract    The reaction of the sodium carbonyl metalate Na[W(CO)3Cp] with the phosphorane (Me3SiCH2)3PBr2 results in the formation of (Me3SiCH2)3PandCp(CO)3WBr or [Cp(CO)3W]2, respectively, depending on the solvent used. The redox reactions between Na[Mo(CO)3Cp] and the arsenic analogue (RCH2)3AsBr2 (R = Ph, Me3Si) yield the products Cp(CO)sMoBr and (RCH2)3As. A mechanism involving radicals is discussed. At elevated temperatures the products react further to give the square pyramidal complexes cts-Cp(CO)2[As(CH2R)3]MBr (1, 2a, b) with loss ofCO. In an analogous manner Cp(CO)3MBr (M = Mo, W) and (RCH2)3E (E = As, Sb) afford compounds ci.s-Cp(CO)2[E(CH2R)3]MBr (2c, 3). The dynamic behaviour of the chiral complexes 1, 2a, b, was investigated by X H NMR spectroscopy. 
  Reference    Z. Naturforsch. 37b, 845—850 (1982); eingegangen am 2. Februar 1982 
  Published    1982 
  Keywords    Transition Metal Nucleophiles, Redox Reaction, Stereospecific CO-Substitution, Dynamic Behaviour 
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 TEI-XML for    default:Reihe_B/37/ZNB-1982-37b-0845.pdf 
 Identifier    ZNB-1982-37b-0845 
 Volume    37 
4Author    Nils Wiberg, Kerstin Amelunxen, Hans-Wolfram Lemer, Heinrich Nöth, Jörg Knizek, Ingo KrossingRequires cookie*
 Title    Supersilylverbindungen der Borgruppenelemente  
 Abstract    , IV [1]. Supersilylelementhalogenide fBu3SiEX2 und (fBu3Si)2EX mit E = Al, Ga, In: Synthesen, Eigenschaften, Strukturen [2] Supersilylated Compounds of the Thirteenth Group, IV [I]. Supersilylelement Halides rBu3SiEX2 and (/Bu3Si)2EX with E = Al, Ga, In: Syntheses, Properties, Structures [2] Water and oxygen sensitive compounds (rBu3SiEX2)2, fBu3SiEX2 Do and (rBu3Si)2EX (E = AI, Ga, In; X = (F), Cl, Br; Do = OR2, NR3) have been synthezised by reaction of EX3 with rBu3SiNa in the absence or presence of donors. In addition, (?Bu3Si)AlBr2, (fBu3Si)2InF and rBu3SiInBr2 were prepared by reaction of AlBr3 with (rBu3Sij2Zn or of (/Bu3Si)2In-In(Si/Bu3)2 with AgF2 and HBr, respectively. The adduct [rBu3SiAlBr2 AlBr3 '/ 2M gBr2]2 is formed from AlBr3 and (fBu3Si)2Mg(THF)2. Thermal decomposition of the compounds in solution or in the gas phase leads to the formation of ?Bu3SiEX2 (from the dimers or the donor adducts) and of fBu3SiX. The Lewis acidity of ?Bu3SiEX2 against donors incre­ ases in the direction Do = Et20 < THF < NEtM e2. Dehalogenation of (/Bu3Si)2ECl with /Bu3SiNa(THF)2 in pentane at room temperature leads to clusters (rBu3Si)4Al2, (fBu3Si)3Ga2*, (fBu3Si)4In2 and (rBu3Si)3Ga2Na(THF)3, reduction of rBu3SiGaCl2 with Na or K in heptane at 100°C to the tetrahedran (rBu3Si)4Ga4. The structures of (rBu3SiGaCl2)2, (fBu3Si)2GaCl, and [/Bu3SiAlBr2 AlBr3-'/2MgBr2]2 have been determined by X-ray structure analysis. 
  Reference    Z. Naturforsch. 53b, 333—348 (1998); eingegangen am 7. November 1997 
  Published    1998 
  Keywords    Supersilylaluminum Halides, Supersilylgallium Halides, Supersilylindium Halides, Acid-base Reactions, Redox-Reactions, X-Ray Data 
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 TEI-XML for    default:Reihe_B/53/ZNB-1998-53b-0333.pdf 
 Identifier    ZNB-1998-53b-0333 
 Volume    53