Journal of the American Chemical Society
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(8) Tran, C. T.; Kim, E. Inorg. Chem. 2012, 51, 10086.
The present studies demonstrate that the degradation
of prototypical [2Fe-2S] clusters by NO in the presence
of H (e–/H+) produces H2S. Proton-coupled electron
transfer (PCET) by cellular H donors such as cysteine
and tyrosine is prevalent in biology. The importance of
PCET reactivity of iron-sulfur clusters has been widely
appreciated in the systems such as CO-ligated [Fe-S]
hydrogeneases28 and the Reiske proteins.29 Our results
here strongly suggest that NO reactivity of prototypical
cysteinate bound [Fe-S] clusters is likely coupled to
PCET chemistry, in which local protein residues or the
millimolar concentrations of intracellular glutathione30
likely play a role in [Fe-S] degradation by NO leading to
the formation of H2S. Therefore, it is conceivable that
iron-sulfur clusters might be one of the intersecting sites
that facilitate crosstalk between NO and H2S.
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(13) {Fe(NO)2}9 follows the Enemark-Feltham notation. Enemark,
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W. F. Inorg. Chem. 2004, 43, 5159. (b) Tsai, F. T.; Chiou, S. J.; Tsai,
M. C.; Tsai, M. L.; Huang, H. W.; Chiang, M. H.; Liaw, W. F. Inorg.
Chem. 2005, 44, 5872. (c) Harrop, T. C.; Tonzetich, Z. J.; Reisner, E.;
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(15) See the Supporting Information
ASSOCIATED CONTENT
Supporting Information. Experimental details and charac-
terizations, CIF for 5. This material is available free of
(16) Lippert, A. R.; New, E. J.; Chang, C. J. J. Am. Chem. Soc.
2011, 133, 10078.
AUTHOR INFORMATION
(17) BDFE (gas phase) for EtSH, tBuSH, and PhSH are 79.1, 78.4,
and 75.3 kcal/mol, respectively.18 The pKa values of EtSH and PhSH
(in H2O) are 10.6 and 6.6.18 Less acidic properties of EtSH and tBuSH
than PhSH are important in ensuring no ligand substitution on 1.
(18) Warren, J. J.; Tronic, T. A.; Mayer, J. M. Chem. Rev. 2010,
110, 6961.
Corresponding Author
Notes
The authors declare no competing financial interest.
(19) We were unable to identify the remaining sulfur-containing
byproduct(s) that should constitute ~40%.
(20) (a) Tsai, M. L.; Liaw, W. F. Inorg. Chem. 2006, 45, 6583. (b)
Huang, H. W.; Tsou, C. C.; Kuo, T. S.; Liaw, W. F. Inorg. Chem.
2008, 47, 2196.
ACKNOWLEDGMENT
This work was supported by the NSF (CHE 1254733).
(21) (a) Manner, V. W.; Markle, T. F.; Freudenthal, J. H.; Roth, J.
P.; Mayer, J. M. Chem. Commun. 2008, 256. (b) Zdilla, M. J.; Dex-
heimer, J. L.; Abu-Omar, M. M. J. Am. Chem. Soc. 2007, 129, 11505.
(22) Spin quantification of the g = 2.004 signal constitutes only ca
20% of what was expected, which may be due to reactivity of
tBu3PhO with unidentified byproducts. The thiyl radical, Ph3CS, is
not detectable under the current experimental conditions.
(23) (a) Reynolds, J. G.; Holm, R. H. Inorg. Chem. 1980, 19, 3257.
(b) Ballmann, J.; Sun, X.; Dechert, S.; Schneider, B.; Meyer, F. Dal-
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(26) Although water has different properties from NO as a ligand,
it is known to affect NO binding kinetics of ferric ion. See references
in Ford, P. C.; Lorkovic, I. M. Chem. Rev. 2002, 102, 993.
(27) The outer-sphere oxidation of phenylthiol by 9 is also plausi-
ble although such a possibility is not included in Scheme 2.
(28) (a) Greco, C.; Bruschi, M.; Fantucci, P.; Ryde, U.; De Gioia,
L. J. Am. Chem. Soc. 2011, 133, 18742. (b) Olsen, M. T.; Rauchfuss,
T. B.; Wilson, S. R. J. Am. Chem. Soc. 2010, 132, 17733.
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