2011, 17, 13358; (e) T. T. Lu, C. H. Chen and W. F. Liaw, Chem.–Eur. J.,
2010, 16, 8088; (f) F. T. Tsai, P. L. Chen and W. F. Liaw, J. Am. Chem.
Soc., 2010, 132, 5290; (g) Z. J. Tonzetich, F. Heroguel, L. H. Do and
S. J. Lippard, Inorg. Chem., 2011, 50, 1570; (h) Z. J. Tonzetich, L. H. Do
and S. J. Lippard, J. Am. Chem. Soc., 2009, 131, 7964; (i) C. E. Tinberg,
Z. J. Tonzetich, H. Wang, L. H. Do, Y. Yoda, S. P. Cramer and
S. J. Lippard, J. Am. Chem. Soc., 2010, 132, 18168; ( j) Z. J. Tonzetich,
H. Wang, D. Mitra, C. E. Tinberg, L. H. Do, F. E. Jenney, Jr.,
M. W. Adams, S. P. Cramer and S. J. Lippard, J. Am. Chem. Soc., 2010,
132, 6914; (k) J. L. Hess, C. H. Hsieh, S. M. Brothers, M. B. Hall and
M. Y. Darensbourg, J. Am. Chem. Soc., 2011, 133, 20426; (l) J. L. Hess,
C. H. Hsieh, J. H. Reibenspies and M. Y. Darensbourg, Inorg. Chem.,
2011, 50, 8541; (m) C. H. Hsieh and M. Y. Darensbourg, J. Am. Chem.
Soc., 2010, 132, 14118; (n) J. H. Wang and C. H. Chen, Inorg. Chem.,
2010, 49, 7644; (o) R. Wang, X. Wang, E. B. Sundberg, P. Nguyen,
G. P. Grant, C. Sheth, Q. Zhao, S. Herron, K. A. Kantardjieff and L. Li,
Inorg. Chem., 2009, 48, 9779.
species by O2 had been observed as early as the 1980s by Postel
and coworkers.29 Although neither the formation of peroxynitrite
nor phenol nitration chemistry were investigated by Postel, oxi-
dation of substrates such as phosphines and olefins was reported
during the oxygenation.29 Since we now learn that peroxynitrite
can be generated from DNICs and O2, it would be worth revisit-
ing Postel’s system to probe the involvement of peroxynitrite and
test the generality of such a reaction.
In summary, we have reported a new {Fe(NO)2}10 dinitrosyl
complex [Fe(dmp)(NO)2] (1) that facilitates nitration of phenol
in the presence of O2. In the absence of phenolic substrates, oxy-
genation of 1 leads to the formation of a nitrato compound,
[Fe2O(NO3)4(dmp)2] (2), which itself is incapable of nitrating
phenols, indicating that a reactive nitrating species forms prior to
the formation of 2. We suggest that a peroxynitrite (ONOO−)
species, which is a powerful nitrating agent and is known to iso-
merize to nitrate (NO3−), is involved in the nitration reactivity
of 1/O2.
13 D. R. Richardson and H. C. Lok, Biochim. Biophys. Acta, 2008, 1780,
638.
14 N. G. Tran, H. Kalyvas, K. M. Skodje, T. Hayashi, P. Moenne-Loccoz,
P. E. Callan, J. Shearer, L. J. Kirschenbaum and E. Kim, J. Am. Chem.
Soc., 2011, 133, 1184.
15 This value falls within the expected range for neutral N-bound DNICs.
See ref. 12h and 12o as well asN. Reginato, C. T. C. McCrory,
D. Pervitsky and L. J. Li, J. Am. Chem. Soc., 1999, 121, 10217;
R. E. Dessy, J. C. Charkoud and A. L. Rheingold, J. Am. Chem. Soc.,
1972, 94, 738.
Acknowledgements
The authors thank Brown University (E.K.), the Camille and
Henry Dreyfus New Faculty Award Program (E.K.), and the
NSF (P.G.W. 1058051) for financial support.
16 S. Goldstein, J. Lind and G. Merenyi, Chem. Rev., 2005, 105, 2457.
17 C15H13.50FeN4.50O6.50, M = 416.65, monoclinic, a = 17.72(3) Å, b =
12.90(2) Å, c = 14.74(3) Å, U = 3359.00(11) Å3, T = 173(2) K, space
group C12/c1, Z = 8, μ = 0.945 mm−1, reflections collected = 13 820,
3314 unique (Rint = 0.0687) which were used in all calculations. The
final wR(F2) was 1.044 (all data).
18 This crystal also incorporates a molecule of acetonitrile not shown in
Fig. 2 whose linear axis also lies on a crystallographic 2-fold axis of
symmetry.
Notes and references
1 H. Lewandowska, M. Kalinowska, K. Brzoska, K. Wojciuk, G. Wojciuk
and M. Kruszewski, Dalton Trans., 2011, 40, 8273.
2 A. F. Vanin, Nitric Oxide, 2009, 21, 1.
19 D. M. Kurtz, Chem. Rev., 1990, 90, 585.
3 J. H. Enemark and R. D. Feltham, Coord. Chem. Rev., 1974, 13, 339.
4 A. J. Vithayathil, J. L. Ternberg and B. Commoner, Nature, 1965, 207,
1246.
20 K. L. Taft, A. Masschelein, S. C. Liu, S. J. Lippard, D. Garfinkelshweky
and A. Bino, Inorg. Chim. Acta, 1992, 198, 627.
21 J. C. Plakatouras, T. Bakas, C. J. Huffman, J. C. Huffman,
V. Papaefthymiou and S. P. Perlepes, J. Chem. Soc., Dalton Trans., 1994,
2737.
22 P. C. Healy, J. M. Patrick and A. H. White, Aust. J. Chem., 1984, 37,
1405.
23 G. R. Wyllie and W. R. Scheidt, Chem. Rev., 2002, 102, 1067.
24 P. B. Critchlow and S. D. Robinson, Coord. Chem. Rev., 1978, 25, 69.
25 In the 18O-labeled 2, nitrato peaks were observed at 1275 and 1502 cm−1
(Δν(NO3) = 11 cm−1 and 8 cm−1, respectively).
5 J. R. Mallard and M. Kent, Nature, 1964, 204, 1192.
6 A. F. Vanin and R. M. Nalbandian, Biofizika, 1965, 10, 167.
7 E. Cesareo, L. J. Parker, J. Z. Pedersen, M. Nuccetelli, A. P. Mazzetti,
A. Pastore, G. Federici, A. M. Caccuri, G. Ricci, J. J. Adams,
M. W. Parker and M. Lo Bello, J. Biol. Chem., 2005, 280, 42172.
8 B. D’Autreaux, O. Horner, J. L. Oddou, C. Jeandey, S. Gambarelli,
C. Berthomieu, J. M. Latour and I. Michaud-Soret, J. Am. Chem. Soc.,
2004, 126, 6005.
9 M. C. Kennedy, W. E. Antholine and H. Beinert, J. Biol. Chem., 1997,
272, 20340.
10 J. C. Woolum, E. Tiezzi and B. Commoner, Biochim. Biophys. Acta,
1968, 160, 311.
11 A. R. Butler and I. L. Megson, Chem. Rev., 2002, 102, 1155.
12 Selected recent examples of DNICs from the research groups of Liaw,12a–f
Lippard,12g–j Darensbourg,12k–m and others12n,o include: (a) S. W. Yeh,
C. W. Lin, Y. W. Li, I. J. Hsu, C. H. Chen, L. Y. Jang, J. F. Lee and
W. F. Liaw, Inorg. Chem., 2012, 51, 4076; (b) Z. S. Lin, F. C. Lo,
C. H. Li, C. H. Chen, W. N. Huang, I. J. Hsu, J. F. Lee, J. C. Horng and
W. F. Liaw, Inorg. Chem., 2011, 50, 10417; (c) T. T. Lu, S. H. Lai,
Y. W. Li, I. J. Hsu, L. Y. Jang, J. F. Lee, I. C. Chen and W. F. Liaw, Inorg.
Chem., 2011, 50, 5396; (d) C. C. Tsou and W. F. Liaw, Chem.–Eur. J.,
26 P. Pacher, J. S. Beckman and L. Liaudet, Physiol. Rev., 2007, 87, 315.
27 C. Szabo, H. Ischiropoulos and R. Radi, Nat. Rev. Drug Discovery, 2007,
6, 662.
28 P. K. Wick, R. Kissner and W. H. Koppenol, Helv. Chim. Acta, 2001, 84,
3057.
29 (a) F. Tomi, H. L. K. Wah and M. Postel, New J. Chem., 1988, 12, 289;
(b) H. L. K. Wah, M. Postel and F. Tomi, Inorg. Chem., 1989, 28, 233;
(c) P. Guillaume, H. L. K. Wah and M. Postel, Inorg. Chem., 1991, 30,
1828; (d) H. L. K. Wah, M. Postel, F. Tomi, F. Agbossou,
D. Ballivettkatchenko and F. Urso, Inorg. Chim. Acta, 1993, 205, 113;
(e) P. Guillaume and M. Postel, Inorg. Chim. Acta, 1995, 233, 109;
(f) V. Munyejabo, P. Guillaume and M. Postel, Inorg. Chim. Acta, 1994,
221, 133.
This journal is © The Royal Society of Chemistry 2012
Dalton Trans., 2012, 41, 7849–7851 | 7851