Electrochemical study of 4-chloroaniline in a water/acetonitrile mixture. A new method for the synthesis of 4-chloro-2-(phenylsulfonyl)aniline and N-(4-chlorophenyl)benzenesulfonamide

Novel fused bis-germatranes containing three hypercoordinated atoms (two Ge and one N) and substituted at the 1,1′-positions with bromo-thienyl groups [(3-bromo-2-thienyl)-, (3,5-dibromo-2-thienyl)-, and 3-(4-bromo)-2-thienyl] have been synthesized from the corresponding triethoxy(thienyl)germanes and tris(1,3-dihydroxypropan-2-yl)amine. The doubly degenerated HOMO and HOMO-1 in these compounds are localized on the thienyl substituents while a 5c-6e hyperbond of the bis-germatranyl core (C–Ge←N→Ge–C system) is only a lower lying HOMO-2. Square-wave pulse voltammetry in CH3CN/0.1 M Bu4NPF6 shows all three compounds to undergo reversible electrochemical oxidation affecting one thienyl substituent. The DFT B3LYP/Lanl2DZ//HF/6-311G(d,p) calculations of their cation radicals suggest the enhancement and shortening of the N→Ge intramolecular dative bond on the side of the oxidized thienyl unit because of the positive charge and the increased acceptor character of the latter; this is accompanied by the loss of the N→Ge dative bond on the side of the non-oxidized substituent and a substantial pyramidalization of the Ge atom.

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Methane Electrochemical Oxidation Pathway over a Ni/YSZ and La0.3Sr0.7TiO3Bi-Layer SOFC Anode

Journal of The Electrochemical Society ◽

10.1149/2.001204jes ◽

2012 ◽

Vol 159 (4) ◽

pp. B361-B367 ◽

Cited By ~ 15

Author(s):

M. A. Buccheri ◽

J. M. Hill

Keyword(s):

Electrochemical Oxidation ◽

Oxidation Pathway ◽

Sofc Anode

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1,n-Radical ions. Photosensitized (electron transfer) and electrochemical oxidation of 1,1,2,2-tetraphenylcyclopropane

Canadian Journal of Chemistry ◽

10.1139/v85-145 ◽

1985 ◽

Vol 63 (4) ◽

pp. 871-881 ◽

Cited By ~ 5

Author(s):

Danial D. M. Wayner ◽

Donald R. Arnold

Keyword(s):

Electron Transfer ◽

Electrochemical Oxidation ◽

Radical Anion ◽

Electrochemical Study ◽

Radical Ions ◽

Reaction Conditions ◽

Aromatic Nitriles ◽

Redox Behaviour ◽

Transfer Study

The photosensitized (electron transfer) and the electrochemical oxidation of 1,1,2,2-tetraphenylcyclopropane (1) have been studied. The products obtained from the photosensitized (electron transfer) study are 1,1,3,3-tetraphenylpropene (2), 1,3,3-triphenylindene (3), tetraphenylallene (4), and 3-methoxy-1,1,3,3-tetraphenylpropene (8). The product ratios are dramatically dependent upon the reaction conditions, particularly sensitizer (aromatic nitriles, tetracyanoethylene, chloranil, and 2,3-dichloro-5,6-dicyanobenzoquinone were used), and solvent. The variations in product ratios are attributed to variations in the redox behaviour of the sensitizer radical anion and upon the basicity and nucleophilicity of the medium. The products in the electrochemical study are 3, 4, and 8. Common intermediates have been identified and a mechanism for the formation of products is proposed.

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