Abstract
Fe(CO)5 is sufficiently stable at 80 °C in benzene solution and its thermal decomposition is not accelerated in the presence of phenyl cinnamate or/and DMF. The decomposition is accelerated by CCl3Br (drastically) and by CCl4 (to a lesser extent). DMF accelerates the reaction of Fe(CO)5 with CCl4. The (FeCl(DMF)5]2+[Cl3FeOFeCl3]2− complex has been isolated as a product; its composition and structure have been determined by X-ray analysis. The obtained data indicate the absence of coordination of DMF or/and an olefin with Fe0 species at the stage preceding oxidation. The mechanisms of the generation of CCl3 radicals in thermal and photochemical Kharash reactions in the presence of Fe(CO)5 are basically different. The probable pathways of the effect of DMF on the rate of the oxidative decomposition of Fe(CO)5 are discussed.
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For Part 2, see Ref. 1.
Translated from IzvestiyaAkademii Nauk. Seriya Khimicheskaya, No. 4, pp. 916–919, April, 1996.
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Tararov, Y.I., Pisarevskii, A.P. & Belokon, Y.N. On the mechanism of the Kharash reaction catalyzed by Fe(CO)5 . Russ Chem Bull 45, 871–874 (1996). https://doi.org/10.1007/BF01431315
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DOI: https://doi.org/10.1007/BF01431315