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The reactions between silver(I) salts and tert-butylacetylene in the presence of different anions (i.e. F−, Cl−, Br−, BF4− Tos− and NO3−) are reported. When fluoride, chloride or bromide salts are present, AgBF4 reacts with tert-butylacetylene to yield the rhombic dodecahedral silver-alkynyl cages [Ag14(C&z.tbnd6;CtBu)12X][BF4] (X=Cl, 1; Br, 2; F, 3). The crystal structure of the fluoride-containing cage is presented in this paper and compared to the previously reported structures of the chloride and bromide-containing cages. In the three structures, the silver atoms are held together by a combination of bridging alkynyl groups and Ag⋯Ag metallophilic interactions. A remarkable feature in the syntheses of these cages is the templating role played by the halide anions. Solution IR spectroscopy and ESI mass spectrometry experiments have demonstrated that the cage structure of compounds 1–3 is retained in solution. When AgTos (Tos=p-toluenesulfonate) and AgNO3 are reacted with tert-butylacetylene (in the absence of halides) the formation of the organometallic polymers [Ag3(C&z.tbnd6;CtBu)2X]n (X=Tos, 4; NO3, 5) is observed. The crystal structure of 4 is here reported. [Copyright &y& Elsevier]

Microwave heating was applied in the oxidative coupling of methane to higher hydrocarbons over alumina supported La2O3/CeO2 catalysts. It was found that microwave heating had a dramatic effect on the reaction when methane was converted into C2 hydrocarbons in the absence of oxygen, with products produced at measured temperatures about 250 °C lower than those observed with conventional heating. It was shown that the reaction in the absence of oxygen occurred primarily in the gas phase and it was the localised heating of the methane that was responsible for the increased reaction rate. However, it was observed that microwave heating did not produce significant “special microwave effects” which affected the product species formed when the oxidative coupling reaction occurred in the presence of oxygen. [Copyright &y& Elsevier]

The oscillatory behaviour over cobalt wire and foil catalysts was examined at atmospheric pressure under various reaction temperatures and argon/methane/oxygen feed gas compositions for the partial oxidation of methane. Rough and porous oxide layers on the catalyst surface were confirmed by scanning electron microscopy (SEM) and X-ray diffraction (XRD) techniques. The results obtained from the experimental studies indicated that the oscillatory behaviour exhibited during methane oxidation was related to the behaviour of the catalyst surface switching back and forth from the reduced state to the oxidised state. The reduction of the oxide layer followed by the almost immediate re-oxidation of the metal can be accounted for only if the oxide layer formed by oxidation is different from the oxide layer existing during reduction. [Copyright &y& Elsevier]

Oscillatory reactions over palladium foil and wire catalysts during the oxidation of methane have been investigated over a wide range of reaction temperatures and argon/methane/oxygen feed gas compositions. Characterisation of the catalyst has also been carried out using scanning electron microscopy (SEM) techniques, which revealed the presence of a porous surface. This suggested that the metal surface has undergone a change since the reaction commenced, and using X-ray powder diffraction (XRD) techniques the palladium phase was shown to be the dominant phase present. Hysteresis phenomena were observed in the activity of the reaction as the temperature was cycled up and down, showing that the metal surface was continually changing throughout the reaction. The activation energies of the reaction during the high reactivity mode, PdO, and low reactivity mode, Pd, were also calculated. Oscillation rates were observed to depend on the dominant surface. Oscillations were frequent when the high reactivity mode was dominant while the activation energy of this mode was found to be low. When the low reactivity mode was dominant, the oscillations were slower and the activation energy was three times larger. The results obtained imply that the behaviour of the palladium surface, switching back and forth from the reduced state to the oxidised state, is responsible for the oscillatory behaviour seen in this system. [Copyright &y& Elsevier]