Conclusions
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1.
An ESR spectroscopic study was carried out at 20°C on the photochemically initiated reaction of Re2(CO)10 with monohalo and polyhalo aliphatic and aromatic compounds.
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2.
In substitution reactions involving breakage of a C-Hal bond, Re(CO)5 is more than three orders of magnitude more active than CpW(CO)3 and more than two or three orders less reactive than Śi(C2H2)2 radicals.
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3.
The rate constants for halogen abstraction by Re(CO)5 radicals increase by two orders of magnitude in going from the chlorides to the analogous bromides and from monohaloalkanes to allyl halides and then to benzyl halides and from α,α-dichloroalkanes toα,α,α-trichloroalkanes.
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4.
Comparison of the rate constants for halogen abstraction by Si(C2H5)3 and Re(CO)5 radicals yields an explanation for the high efficiency of the Re2(CO)10 + HSi(C2H5)3 system relative to Re2(CO)10 alone for the generation ofα-chloro radicals.
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Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp. 1031–1037, May, 1986.
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Gasanov, R.G., Sadykhov, É.G. & Freidlina, R.K. Rate constants of the reactions of Re(CO)5 radicals with organic halides determined using esr spectroscopy. Russ Chem Bull 35, 936–941 (1986). https://doi.org/10.1007/BF00955353
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DOI: https://doi.org/10.1007/BF00955353