Journal of the American Chemical Society
Communication
absence of an HNO target, reaction of 1 and H+ ultimately leads
to the Co-dinitrosyl complex 3 (via intermediate 4). To our
knowledge the reaction of 1 and H+ is the first example of a
{CoNO}8 complex that specifically behaves as an HNO donor to
known HNO targets (FeIII-heme and Ph3P). Proton-induced
formation of other signaling molecules such as H2S has been
observed with synthetic 2Fe-2S clusters and excess NO.32 In
contrast, 1 alone does not exhibit any reactivity from temper-
atures ranging 298−310 K, emphasizing the importance of HNO
versus NO− and the underexplored potential of metal nitrosyls as
HNO donors. Furthermore, these results confirm that {CoNO}8
complexes are not inert and function as sources of HNO under
specific pH conditions, thereby opening up a new frontier in
HNO donor research.
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ASSOCIATED CONTENT
■
S
* Supporting Information
Details of the syntheses, reactivity, spectroscopic, and crystallo-
graphic (CIF) results. This material is available free of charge via
AUTHOR INFORMATION
■
Corresponding Author
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
T.C.H. thanks the NSF (CHE-0953102) and UGA for financial
support. T.L.S. and A.V.R acknowledge the NIH and the
American Heart Association/Friedreich’s Ataxia Research
Alliance awards DK068139 and 12PRE11720005, respectively.
XAS was collected at the National Synchrotron Radiation
Laboratory (NSLS) on beamline X3b. NSLS is supported by the
U.S. DOE, Division of Materials Sciences and Division of
Chemical Sciences (contract no. DEAC02-98CH10886). J.L.U.
and R.J.U. thank the Office of the Vice President for Research
(OVPR) and the Office of the Provost at UGA for financial
support. We wish to thank Dr. Dennis R. Phillips, Dr. Chau-Wen
Chou, and Prof. I. Jonathan Amster for their assistance with high-
resolution MS experiments. We acknowledge Henry
Niedermaier for assistance with NMR.
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2009, 11, 2719. (b) Reisz, J. A.; Zink, C. N.; King, S. B. J. Am. Chem. Soc.
2011, 133, 11675.
(25) (a) Oxidation−reduction reactions have been previously shown
to occur in coordination complexes when examined by ESI-MS.
(b) Henderson, W.; McIndoe, J. S. The ESI MS Behaviour of
Coordination Complexes. In Mass Spectrometry of Inorganic and
Organometallic Compounds; John Wiley & Sons Ltd: Chichester, 2005.
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(27) According to peak integrations, 3 makes up ∼20% of the reaction
mixture (Figure S12). We attribute the low amount of 3 due to its poor
solubility and the large amount of unreacted 1.
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