Plea sDe a dl t oo nn oT tr aa nd sj au cs tt i om n as rgins
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DOI: 10.1039/C9DT02834J
ARTICLE
Journal Name
III
II
The idea of M ‐nitrosyl formation from a M ‐ONOH intermediate 12. R. Radi, Proc. Natl. Acad. Sci. U S A, 2004, 101, 4003‐4008.
2 2
would be feasible by either (i) the release of H O
(Scheme 1, reaction 13. B. Kalyanaraman, Proc. Natl. Acad. Sci. U S A, 2004, 101, 11527‐
II
11528.
IIa) or (ii) the examples where M ‐ONOH transformed to a M‐NO +
4
6
II
–
+
14. P. C. Dedon and S. R. Tannenbaum, Arch. Biochem. Biophys.,
2004, 423, 12‐22.
15. B. A. Averill, Chem. Rev., 1996, 96, 2951‐2964.
H
2
O. The mechanistic steps for the reaction of Co (NO
are given in Scheme 3. As known for NiR enzyme activity,
electrophilic addition of H to 2 will produce Co ‐ONOH (3) (Scheme
, reaction II). In contrast to the reported NiR enzyme activity where
NO formed by the heterolytic cleavage of ON‐OH bond with the
O, for the first time, the formation of nitrosyl complex
was observed by the homolytic cleavage of ON‐OH
moiety with simultaneous electron transfer from Co to NO (Scheme
2
) with H
4
6
+
II
1
6. E. I. Tocheva, F. I. Rosell, A. G. Mauk and M. E. Murphy, Science,
1
2004, 304, 867‐870.
2
4
7
17. N. Lehnert, T. C. Berto, M. G. I. Galinato and L. E. Goodrich, in
Handbook of Porphyrin Science, eds. K. Kadish, K. Smith and R.
Guilard, World Scientific Publishing, Singapore, 2011, p. 1.
8. T. B. McCall, N. K. Boughton‐Smith, R. M. Palmer, B. J. Whittle
and S. Moncada, Biochem. J., 1989, 261, 293‐296.
removal of H
4) and H
2
(
2
O
2
II
1
1
2
2
2
2
2
1, reaction IIa).
In summary, we have demonstrated the reaction of [(12‐
)] (2) with acid (H ) and/or base (OH ) (Scheme 1). For
the first time, we have demonstrated the clear formation of Co ‐
9. R. G. Knowles and S. Moncada, Biochem. J., 1994, 298 ( Pt 2), 249‐
II
+
+
–
TMC)Co (NO
2
2
58.
0. J. Brooks and D. Keilin, Proc. Royal Soc. Lond. B, 1937, 123, 368‐
82.
1. M. P. Doyle and J. W. Hoekstra, J. Inorg. Biochem., 1981, 14, 351‐
58.
III
8
III
– 2+
2 2
nitrosyl complex ({CoNO} ), [(12‐TMC)Co (NO )] (4), and H O in
3
+
II
the reaction of 2 with one fold H via a Co ‐ONOH (3) intermediate.
Similar results, the formation of metal nitrosyl and hydrogen
peroxide, were also observed in the aqueous system. However, NiR
3
2. P. R. Gardner, A. M. Gardner, L. A. Martin and A. L. Salzman, Proc.
Natl. Acad. Sci. U S A, 1998, 95, 10378‐10383.
3. T. S. Kurtikyan, A. A. Hovhannisyan, A. V. Iretskii and P. C. Ford,
Inorg. Chem., 2009, 48, 11236‐11241.
4. B. C. Sanders, S. M. Hassan and T. C. Harrop, J. Am. Chem. Soc.,
2014, 136, 10230‐10233.
25. S. Kundu, W. Y. Kim, J. A. Bertke and T. H. Warren, J. Am. Chem.
Soc., 2017, 139, 1045‐1048.
2
0
48
heme protiens and Co substituted Mb generates NO and water
from nitrite. In contrast to the nitrite reduction reaction by H , the
reaction of 2 with OH do not form nitrosyl complex (4). It is
O formation involves a distinctive pathway
2 2
of ON‐OH homolytic cleavage. The present study is the first ever
report where a Co ‐ONOH intermediate generates {CoNO} + H
products, adding an entirely new mechanistic insight, and propose
+
–
important to note that H
II
8
2
O
2
the additional pathway for nitrite reduction reactions and the 26. L. Cheng, D. R. Powell, M. A. Khan and G. B. Richter‐Addo, Chem
generation of hydrogen peroxide in bio‐systems.
Comm, 2000, 0, 2301‐2302.
2
7. A. K. Patra, R. K. Afshar, J. M. Rowland, M. M. Olmstead and P. K.
Mascharak, Angew. Chem., Int. Ed., 2003, 42, 4517‐4521.
8. S. Hong, J. J. Yan, D. G. Karmalkar, K. D. Sutherlin, J. Kim, Y. M.
Lee, Y. Goo, P. K. Mascharak, B. Hedman, K. O. Hodgson, K. D.
Karlin, E. I. Solomon and W. Nam, Chem. Sci., 2018, 9, 6952‐6960.
9. J. Heinecke and P. C. Ford, Coordin Chem Rev, 2010, 254, 235‐
Conflicts of interest
There are no conflicts to declare.
2
2
2
47.
Acknowledgments
This work was supported by Grants‐in‐Aid (Grant No.
EEQ/2016/000466) from SERB‐DST. Special thanks to Dr. Sayam Sen
Gupta (IISER Kolkata) for EPR facility.
3
3
0. A. P. Hunt and N. Lehnert, Acc. Chem. Res., 2015, 48, 2117‐2125.
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1
3
3
3
3. P. Kumar, Y. M. Lee, Y. J. Park, M. A. Siegler, K. D. Karlin and W.
Nam, J. Am. Chem. Soc., 2015, 137, 4284‐4287.
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