Browsing by Author "Naito, Shuichi"

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    Catalytic Activity and Electron Configuration of the EDA Complexes of Phthalocyanine with Alkali Metals: Hydrogen Adsorption and the H2—D2 Exchange Reaction
    (Journal of the Chemical Society : Faraday Transaction - I. The Chemical Society, London. 1972, 68 (8), 1972) Naito, Shuichi; Ichikawa, Masaru
    Hydrogen adsorption and H2—D2 exchange reaction on the stoichiometric EDA (electron donor-acceptor) complexes of various phthalocyanines with alkali metals (Li, Na, K, Rb) were studied and their behaviour correlated with the electronic structure of the complexes. It was demonstrated that the activity of the complexes for the HZ—D2 exchange reaction, D2+ HZ ⇌ HD + DZ, where HZ represents the EDA complexes of phthalocyanine, was only dependent upon the number of electrons donated to the π-conjugated system of the ligand, irrespective of the kind of central metal ion. On the other hand, the H2—D2 exchange reaction was markedly affected by the central metal cations, which suggests that the hydrogen dissociation takes place within the crystal field of the metal ions The effect of preadsorbed carbon monoxide on the hydrogen chemisorption and the exchange reaction was also studied, and from these results, the nature of the reaction sites discussed.
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    Microwave Spectroscopic Studies of Hydrogen Exchange, Isomerization and Hydrogenation of Unsaturated Hydrocarbons on the Stoichiometric Electron Donor-Acceptor Complexes of Phthalocyanine with Alkali Metals
    (Journal of the Chemical Society : Faraday Transaction - I. The Chemical Society, London. 1973, 69 (4), 1973) Naito, Shuichi; Ichikawa, Masaru; Saito, Shuji
    Hydrogen exchange, isomerization and hydrogenation of olefins, such as C2H4, C3H6 and C4H8, was studied over the stoichiometric electron donor–acceptor (EDA) complexes of various phthalocyanines with alkali metals (Li, Na, K). The mass and microwave spectroscopic techniques have been shown to be effective for determining not only the deuterium content but also its distribution in the [2H1] and [2H2]-species of the reactant and product molecules. It was accordingly concluded that these three reactions proceed through the same reaction intermediate; the half-hydrogenated state of the olefins, and that the rate-determining step is the process where the π-coordinated olefin becomes the σ-coordinated half-hydrogenated state. The chemisorbed state of the olefins and the mechanisms of these reactions were correlated with the electron configuration of the EDA complexes.