G. Metzker et al. / Inorganica Chimica Acta 394 (2013) 765–769
769
[4] D.A. Wink, M. Feelisch, J.M. Fukuto, D. Chistodoulou, D. Jourd’heuil, M.B.
Grisham, Y. Vodovotz, J.A. Cook, M. Krishna, W.G. DeGraff, S. Kim, J. Gamson,
J.B. Mitchell, Arch. Biochem. Biophys. 351 (1998) 66.
[5] J.M. Fukuto, A.J. Hobbs, L.J. Ignarro, Biochem. Biophys. Res. Commum. 196
(1993) 707.
[6] J.M. Fukuto, K. Chiang, R. Hszieh, P. Wong, G. Chaudhuri, J. Pharmacol. Exp.
Ther. 263 (1992) 546.
[7] P.C. Ford, I.M. Lorkovic, Chem. Rev. 102 (2002) 993.
[8] P.G. Wang, T.B. Cai, N. Taniguchi (Eds.), Nitric Oxide Donors For
Pharmaceutical and Biological Applications, Wiley-VCH, Weinheim, 2005.
[9] P.G. Wang, M. Xian, X. Tang, X. Wu, Z. Wen, T. Cai, A.J. Janczuk, Chem. Rev. 102
(2002) 1091.
[10] M.R. Miller, I.L. Megson, Br. J. Pharmacol. 151 (2007) 305.
[11] J.C. Irvine, R.H. Ritchie, J.L. Favaloro, K.L. Andrews, R.E. Widdop, B.K. Kemp-
Harper, Trends Pharmacol. Sci. 29 (2008) 601.
[12] J.F. DuMond, S.B. King, Antioxid. Redox Signal. 14 (2011) 1637.
[13] A.C. Montenegro, V.T. Amorebieta, L.D. Slep, D.F. Martin, F. Roncaroli, D.H.
Murgida, S.E. Bari, J.A. Olabe, Angew. Chem., Int. Ed. 48 (2009) 4213.
[14] J.C. Toledo, H.A.S. Silva, M. Scarpellini, V. Mori, A.J. Camargo, M. Bertotti, D.W.
Franco, Eur. J. Inorg. Chem. (2004) 1879.
[15] E. Tfouni, M. Krieger, B.R. McGarvey, D.W. Franco, Coord. Chem. Rev. 236
(2003) 57.
[16] E. Tfouni, F.G. Doro, L.E. Figueiredo, J.C.M. Pereira, G. Metzker, D.W. Franco,
Curr. Med. Chem. 17 (2010) 3643.
[17] J.C.M. Pereira, V. Carregaro, D.L. Costa, J.S. Silva, F.Q. Cunha, D.W. Franco, Eur. J.
Med. Chem. 45 (2010) 4180.
[18] D.D. Perrin, W.L.F. Armarego, D.R. Perrin, Purification of Laboratory Chemicals,
Pergamon Press, Elmsford, 1980.
[19] D.F. Shriver, The Manipulation of Air-Sensitive Compound, McGraw-Hill, New
York, 1969.
[20] L.H. Vogt, J.L. Katz, S.E. Wiberley, Inorg. Chem. 4 (1965) 1157.
[21] L.G.F. Lopes, E.E. Castellano, A.G. Ferreira, C.U. Davanzo, M.J. Clarke, D.W.
Franco, Inorg. Chim. Acta 359 (2005) 2883.
[22] A.D. Ostrowski, S.J. Deakin, B. Azhar, T.W. Miller, N. Franco, M.M. Cherney, A.J.
Lee, J.N. Burstin, J.M. Fukuto, I.L. Megson, P.C. Ford, J. Med. Chem. 53 (2010) 715.
[23] G. Metzker, J.C. Toledo, F.C.A. Lima, A. Magalhães, D.R. Cardoso, D.W. Franco, J.
Braz. Chem. Soc. 21 (2010) 1266.
[24] M. Lovric, S. Komorsky-Lovric, J. Electroanal. Chem. 248 (1988) 239.
[25] M.J. Frisch, G.W. Trucks, H.B. Schlegel, G.E. Scuseria, M.A. Robb, J.R. Cheeseman,
J.A Montgomery Jr., T. Vreven, K.N. Kudin, J.C. Burant, J.M. Millam, S. S. Iyengar,
J. Tomasi, V. Barone, B. Mennucci, M. Cossi, G. Scalmani, N. Rega, G.A.
Petersson, H. Nakatsuji, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa,
M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, M. Klene, X. Li, J.E. Knox,
H.P. Hratchian, J.B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R.E.
Stratmann, O. Yazyev, A.J. Austin, R. Cammi, C. Pomelli, J.W. Ochterski, P.Y.
Ayala, K. Morokuma, G.A. Voth, P. Salvador, J.J. Dannenberg, V.G. Zakrzewski, S.
Dapprich, A.D. Daniels, M.C. Strain, O. Farkas, D.K. Malick, A.D. Rabuck, K.
Raghavachari, J.B. Foresman, J.V. Ortiz, Q. Cui, A.G. Baboul, S. Clifford, J.
Cioslowski, B. B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R.L.
Martin, D.J. Fox, T. Keith, M.A. Al-Laham, C.Y. Peng, A. Nanayakkara, M.
Challacombe, P.M.W. Gill, B. Johnson, W. Chen, M.W. Wong, C. Gonzalez, J.A.
Pople, Gaussian, Inc., Wallingford, CT, 2004.
As observed above, taking in account the results obtained with
Eu2+, S2O42ꢀ and Zn(Hg), the reductant potential is a necessary but
not sufficient condition for the nitroxyl formation. The intrinsic
reaction mechanism would be relevant to define the products of
the reaction. This is the case for the reaction between ruthenium
nitrosyl complexes and cysteine, a one electron reductant, [46]
for which was postulated the formation of an adduct containing
two cysteine molecules and one ruthenium nitrosyl complex,
yielding HNO as a final product. This subject is under investigation
at our Laboratory.
There are reports in the literature [36,47] of bonded NO- to
ruthenium complexes. The complex [RuCl(NO)2(P(C6H5)3)2]+ exhi-
bit a well documented example of fluxional interchange between
NOꢀ and NO+ ligands; and the complex [Ru(NO)Hedta]2- interest-
ing example of coordinated singlet NO-. However these compounds
are usually robust. Kinetic data on nitroxyl dissociation and exam-
ples of inorganic HNO donors, besides the Angeli’s Salt are not
abundant [1,3,12]. The formation of [Fe(CN)5HNO]3ꢀ with the sub-
sequent HNO liberation is described to occur, but only in presence
of excess of CN- to retard the trans cyanide ion dissociation [13].
Recently was reported the electrochemical reduction of the ni-
tric oxide ligand in cis-[Ru(NO)(Cl2)(dppp)(py)]PF6 without change
in the coordination sphere [48]. The interpretation of this process
at more negative potentials than the one attributed for the
[RuNO]3+/[RuNO]2+ couple was attributed to the formation of the
nitroxyl ligand. However, since no strong trans labilizing ligand
are present in the coordination sphere, the nitroxyl ligand remains
coordinated to the metal center, which would limit these com-
pounds eventual applications as a HNO donors.
It is likely the ability to generate NO and HNO upon controlled
reduction, described for trans-[Ru(NO)(NH3)4(P(OEt)3)]3+ would be
also observed for the other phosphite complexes of the series
where P(III) = P(OR)3, P(OR)2(OH) and P(OH)3, all strong trans labi-
lizing ligands. The present findings are an additional incentive for
tailoring phosphite nitrosyl complexes more resistant to nucleo-
philic attack [23,49] and therefore more stable in a wide range of
pH. This subject is now under investigation and results will be re-
ported later.
4. Conclusion
[26] W. Kohn, L.J. Sham, Phys. Rev. 140 (1965) A1133.
[27] C. Lee, W. Yang, R.G. Parr, Phys. Rev. B 37 (1998) 785.
[28] A.D. Becke, J. Chem. Phys. 98 (1993) 5648.
[29] P.J. Hay, W.R. Wadt, J. Chem. Phys. 82 (1985) 270.
[30] W.R. Wadt, P.J. Hay, J. Chem. Phys. 82 (1985) 284.
According to the experimental data, trans-[Ru(NO)(NH3)4-
(P(OEt)3)]3+ ion behaves as a fast NO and or HNO donor, which
could be selectivity tuned through the judicious choice of the elec-
trochemical potential or the chemical reductant.
[31] P.J. Hay, W.R. Wadt, J. Chem. Phys. 82 (1985) 299.
[32] E.D. Glendening, J.K. Badenhoop, A.E. Reed, J.E. Carpenter, J.A. Bohmann, C.M.
Morales, F. Weihold, NBO 3.0, Theoretical Chemistry Institute, University of
Wisconsin, Madison, 2001.
[33] E. Cances, B. Mennucci, J. Tomasi, J. Chem. Phys. 107 (1997) 3032.
[34] A.E. Reed, F. Weinhold, J. Chem. Phys. 83 (1985) 1736.
[35] A.E. Reed, L.A. Curtiss, F. Weinhold, Chem. Rev. 88 (1988) 899.
[36] C.G. Pierpont, D.G. Van Derveer, W. Durland, R. Eisenberg, J. Am. Chem. Soc. 92
(1970) 4760.
[37] M.D. Bartberger, W. Liu, E. Ford, K.M. Miranda, C. Switzer, J.M. Fukuto, P.J.
Farmer, D.A. Wink, K.N. Houk, Proc. Natl. Acad. Sci. USA 99 (2002) 10958.
[38] V. Shafirovich, S.V. Lymar, Proc. Natl. Acad. Sci. USA 99 (2002) 7340.
[39] C. Gossens, A. Dorcier, P.J. Dyson, U. Rothlisberg, Organomettallics 26 (2007)
3969.
Acknowledgments
The authors acknowledge the Brazilian agencies FAPESP, CAPES
and CNPq for their financial support. The authors also thank A.N.
Chiba and Professor E. Tfouni (FFCLRP-USP) for the NOA
measurements.
[40] M.D. Liptak, G.C. Shields, J. Am. Chem. Soc. 123 (2001) 7314.
[41] R.B. Peters, D.G. Fischer, Quantitative Chemical Analysis, W.B. Saunders
Company, Philadelphia, 1969.
[42] N.S. Hush, J. Blackledge, J. Electroanal. Chem. 5 (1963) 420.
[43] F.A. Cotton, G. Wilkinson, C.A. Murillo, M. Bochmann, Advanced Inorganic
Chemistry, Wiley-Interscience, New York, 1999.
Appendix A. Supplementary material
Supplementary data associated with this article can be found, in
[44] B. Wang, X. Li, Anal. Chem. 70 (1998) 2181.
[45] D.W. Franco, H. Taube, Inorg. Chem. 17 (1978) 571.
References
[46] F. Roncaroli, J.A. Olabe, Inorg. Chem. 44 (2005) 4719.
[47] Y. Chen, F.T. Lin, R.E. Shepherd, Inorg. Chem. 38 (1999) 973.
[48] C.C. Golfeto, G. Von Poelhsitz, H.S. Selistre-de-Araújo, M.P. Araujo, J. Ellena, E.E.
Castellano, L.G.L. Lopes, I.S. Moreira, A.A. Batista, J. Inorg. Biochem. 104 (2010)
489.
[1] J.M. Fukuto, C.H. Switzer, K.M. Miranda, D.A. Wink, Annu. Rev. Pharmacol.
Toxicol. 45 (2005) 335.
[2] C.H. Switzer, W. Flores-Santana, D. Mancardi, S. Donzelli, D. Basudhar, L.A.
Ridnour, K.M. Miranda, J.M. Fukuto, N. Paolocci, D.A. Wink, Biochim. Biophys.
Acta 1787 (2009) 835.
[49] D.R. Truzzi, A.G. Ferreira, S.C. Silva, E.E. Castellano, F.C.A. Lima, D.W. Franco,
Dalton Trans. 40 (2011) 12917.
[3] K.M. Miranda, Coord. Chem. Rev. 249 (2005) 433.