Abstract
The kinetics of thermal reactions of the photochemically-generated species [W(CN)7OH]4− and [W(CN)6–(CNH)(H2O)]2− with 5–nitro-1,10–phenanthroline (nitrophen) in basic and acidic media, respectively, were studied in buffer solutions at pH 4.2–10.6 and ionic strength 7.5×10−2kg−1 at 20°C. The quantum yield for the formation of the photoproduct was calculated and found to depend upon pH and the ligand and [W(CN)8]4− concentrations. The rate constants and quantum yields were less compared with 1,10–phenanthroline due to the electron-withdrawing inductive effect of the nitro group in nitrophen, which makes the latter a weaker ligand. The pseudo-first-order rate constant and quantum yield values in acidic media are higher than in basic media and the mechanisms of the photochemical substitution are different in the two media.
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Thaker, B.T., Kaur, H. & Thaker, P. Photoexcitation of the potassium octacyanotungstate(IV)· 5–nitro-1,10–phenanthroline system: kinetics and mechanism of the reaction. Transition Metal Chemistry 23, 33–36 (1997). https://doi.org/10.1023/A:1006945615324
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DOI: https://doi.org/10.1023/A:1006945615324