Mechanism of activation and catalysis of chemiluminescence by Eu(fod)3 chelate in thermal decomposition of adamantylideneadamantane-1,2-dioxetane |
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Authors: | A. I. Voloshin G. L. Sharipov V. P. Kazakov G. A. Tolstikov |
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Abstract: | Complexation of the chelate both with dioxetane and with adamantanone (2), the product of decomposition of dioxetane, have an important effect on chemiluminescence (CL) in thermal decomposition of adamantylideneadamantane-1,2-dioxetane (1) in the presence of Eu(fod)3 chelate. The stability constants of Eu(fod)3·1 and Eu(fod)3·2 complexes were obtained. It was found that Eu(fod)3 catalyzes and activates chemiluminescent decomposition of1. The rate constant (k2) of decomposition of the Eu(III)·1 complex was determined from the kinetics of quenching of CL, and the activation parameters were determined from the temperature curve. Luminescence from the5D1-level of the Eu(III) ion was detected in the CL spectrum and was correlated with direct (bypassing the triplet of the ligand) transfer of excitation energy from2t* to the luminescent levels of Eu(III) in the geometrically distorted complex Eu(fod)3·2.Institute of Organic Chemistry, Ural Branch, Russian Academy of Sciences, 450054 Ufa. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 5, pp. 1056–1063, May, 1992. |
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Keywords: | chemiluminescence adamantylideneadamantane-1,2-dioxetane Eu(fod)3 catalysis |
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