Absolute rate constants were determined for the abstraction of hydrogen atoms from (OC)(3)Fe(mu-SH)(2)Fe(CO)(3) (Fe(2)S(2)H(2)) and (OC)(3)Fe(mu-SCH(3))(mu-SH)Fe(CO)(3) (Fe(2)S(2)MeH) by benzyl radicals in benzene. From the temperature-dependent rate data for Fe(2)S(2)H(2), DeltaH(++) and DeltaS(++) were determined to be 2.03 +/- 0.56 kcal/mol and -19.3 +/- 1.7 cal/(mol K), respectively, giving k(abs) = (1.2 +/- 0.49) x 10(7) M(-1) s(-1) at 25 degrees C. For Fe(2)S(2)MeH, DeltaH(++) and Delta...Expand abstract
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Activation of the S-H group in Fe(mu(2)-SH)Fe clusters: S-H bond strengths and free radical reactivity of the Fe(mu(2)-SH)Fe cluster.
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