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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.

Abstract:

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...

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Publisher copy:
10.1021/ja904602p

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Institution:
University of Oxford
Department:
Oxford, MSD, Clinical Medicine
Role:
Author
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Journal:
Journal of the American Chemical Society
Volume:
131
Issue:
42
Pages:
15212-15224
Publication date:
2009-10-05
DOI:
EISSN:
1520-5126
ISSN:
0002-7863
URN:
uuid:a20271f5-cc5e-4412-b69c-4de0ed78f9d2
Source identifiers:
420488
Local pid:
pubs:420488
Language:
English

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