Inorg. Chem. 2007, 46, 5465−5467
Dioxygen Activation by Diiminodipyrromethane Complexes of Ni, Pd,
and Pt
Evgeny A. Katayev,*,† Kay Severin,*,‡ Rosario Scopelliti,‡ and Yuri A. Ustynyuk§
A. N. NesmeyanoV Institute of Organoelement Compounds RAS, VaViloVa st. 28, 119991 Moscow,
Russian Federation, Institut des Sciences et Inge´nieries Chimiques, Ecole Polytechnique Fe´de´rale
de Lausanne (EPFL), 1015 Lausanne, Switzerland, and Department of Chemistry, M. V.
LomonosoV Moscow State UniVersity, Leninskie gory 1/3, 119992 Moscow, Russian Federation
Received April 3, 2007
Diiminodipyrromethane complexes of Ni, Pd, and Pt are able to
activate O2, resulting in a metal-dependent autoxidation of the
ligand.
and Cu,8 to name a few. Much effort has been devoted to
complexes with porphyrin ligands because they resemble the
naturally occurring heme complexes and because of their
favorable physicochemical properties (low redox potential
and high stability).9 Multidentate ligands based on dipyr-
romethane fragments are structurally related to porphyrins,
but the reactivity of the corresponding transition-metal
complexes toward O2 is largely unexplored.10,12 In the
following, we describe the synthesis and the reactivity of
novel diiminodipyrromethane complexes of Ni, Pd, and Pt.
It is shown that the complexes are able to activate O2,
resulting in a metal-dependent autoxidation of the ligand.
O2 activation by transition-metal complexes is of prime
importance in the context of bioinorganic chemistry1 and in
the area of preparative organic chemistry.2 Several synthetic
complexes have been reported that are able to activate
molecular oxygen in interesting stoichiometric or catalytic
reactions. This includes complexes of V,3 Fe,4 Ru,5 Os,6 Pd,7
Recently, it has been shown by us11 and others12 that
iminopyrroles and diiminodipyrromethanes are suited ligands
for group 10 metal complexes. For the present study, we
have synthesized NiII, PdII, and PtII complexes of the novel
tetradentate ligand 2. Ligand 2 was obtained by acid-
catalyzed condensation of 2,2′-(5-formyl-3-methyl-4-eth-
* To whom correspondence should be addressed. E-mail: katayev@
ineos.ac.ru (E.A.K.), kay.severin@epfl.ch (K.S.).
† A. N. Nesmeyanov Institute of Organoelement Compounds RAS.
‡ Ecole Polytechnique Fe´de´rale de Lausanne.
§ M. V. Lomonosov Moscow State University.
(1) (a) Kryatov, S. V.; Rybak-Akimova, E. V.; Schindler, S. Chem. ReV.
2005, 105, 2175-2226. (b) Decker, A.; Solomon, E. I. Curr. Opin.
Chem. Biol. 2005, 9, 152-163. (c) Costas, M.; Mehn, M. P.; Jensen,
M. P.; Que, L., Jr. Chem. ReV. 2004, 104, 939-986. (d) Meunier, B.;
de Visser, S. P.; Shaik, S. Chem. ReV. 2004, 104, 3947-3980. (e)
Bugg, T. D. H. Curr. Opin. Chem. Biol. 2001, 5, 550-555.
(2) (a) Schultz, M. J.; Sigman, M. S. Tetrahedron 2006, 62, 8227-8241.
(b) Punniyamurthy, T.; Velusamy, S.; Iqbal, J. Chem. ReV. 2005, 105,
2329-2363. (c) Bakac, A. AdV. Inorg. Chem. 2004, 55, 1-59.
(3) (a) Pawar, V. D.; Bettigeri, S.; Weng, S.-S.; Kao, J.-Q.; Chen, C.-T.
J. Am. Chem. Soc. 2006, 128, 6308-6309. (b) Maeda, Y.; Kakiuchi,
N.; Matsumura, S.; Nishimura, T.; Kawamura, T.; Uemura, S. J. Org.
Chem. 2002, 67, 6718-6724.
(8) (a) Lewis, E. A.; Tolman, W. B. Chem. ReV. 2004, 104, 1047-1076.
(b) Zhang, C. X.; Liang, H.-C.; Kim, E.-i.; Shearer, J.; Helton, M. E.;
Kim, E.; Kaderli, S.; Incarvito, C. D.; Zuberbu¨hler, A. D.; Rheingold,
A. L.; Karlin, K. D. J. Am. Chem. Soc. 2003, 125, 634-635. (c)
Chaudhuri, P.; Hess, M.; Weyhermu¨ller, T.; Wieghardt, K. Angew.
Chem., Int. Ed. 1999, 38, 1095-1098. (d) Chaudhuri, P.; Hess, M.;
Flo¨rke, U.; Wieghardt, K. Angew. Chem., Int. Ed. 1998, 37, 2217-
2220. (e) Marko´, I. E.; Giles, P. R.; Tsukazaki, M.; Brown, S. M.;
Urch, C. J. Science 1996, 274, 2044-2046.
(9) (a) Woggon, W.-D. Acc. Chem. Res. 2005, 38, 127-136. (b) Groves,
J. T.; Shalyaev, K.; Lee, J. In The Porphyrin Handbook; Kadish, K.
M., Smith, K. M., Guilard, R., Eds.; Academic Press: New York,
2000; Vol. 4, pp 17-40.
(4) (a) Kim, S. O.; Sastri, C. V.; Seo, M. S.; Kim, J.; Nam, W. J. Am.
Chem. Soc. 2005, 127, 4178-4179. (b) Carson, E. C.; Lippard, S. J.
J. Am. Chem. Soc. 2004, 126, 3412-3413. (c) MacBeth, C. E.;
Golombek, A. P.; Young, V. G., Jr.; Yang, C.; Kuczera, K.; Hendrich,
M. P.; Borovik, A. S. Science 2000, 289, 938-941.
(5) (a) Huynh, H. V.; Witham, L. M.; Lasker, J. M.; Wetzler, M.; Mort,
B.; Jameson, D. L.; White, P. S.; Takeuchi, K. J. J. Am. Chem. Soc.
2003, 125, 308-309. (b) Csjernyik, G.; EÄ ll, A. H.; Fadini, L.; Pugin,
B.; Ba¨ckvall, J.-E. J. Org. Chem. 2002, 67, 1657-1662. (c) Dijksman,
A.; Marino-Gonza´lez, A.; i Payeras, A. M.; Arends, I. W. C. E.;
Sheldon, R. A. J. Am. Chem. Soc. 2001, 123, 6826-6833. (d)
Neumann, R.; Dahan, M. Nature 1997, 388, 353-355. (e) Groves, J.
T.; Quinn, R. J. Am. Chem. Soc. 1985, 107, 5790-5792.
(10) For reviews on expanded porphyrins, see: (a) Sessler, J. L.; Tomat,
E. Acc. Chem. Res. 2007, 40, 371-379. (b) Shimizu, S.; Osuka, A.
Eur. J. Inorg. Chem. 2006, 1319-1335. (c) Sessler, J. L.; Seidel, D.
Angew. Chem., Int. Ed. 2003, 42, 5134-5175.
(11) Katayev, E. A.; Ustynyuk, Y. A.; Lynch, V. M.; Sessler, J. L. Chem.
Commun. 2006, 4682-4684.
(12) (a) Liang, H.; Liu, J.; Li, X.; Li, Y. Polyhedron 2004, 23, 1619-
1627. (b) Iverson, C. N.; Carter, C. A. G.; Baker, R. T.; Scollard, J.
D.; Labinger, J. A.; Bercaw, J. E. J. Am. Chem. Soc. 2003, 125,
12674-12675. (c) Givaja, G.; Blake, A. J.; Wilson, C.; Schro¨der, M.;
Love, J. B. Chem. Commun. 2003, 2508-2509. (d) Givaja, G.; Volpe,
M.; Edwards, M. A.; Blake, A. J.; Wilson, C.; Schro¨der, M.; Love, J.
B. Angew. Chem., Int. Ed. 2007, 46, 584-586. (e) Bacchi, A.; Carcelli,
M.; Gabba, L.; Ianelli, S.; Pelagatti, P.; Pelizzi, G.; Rogolino, D. Inorg.
Chim. Acta 2003, 342, 229-235.
(6) (a) Do¨bler, C.; Mehltretter, G.; Sundermeier, U.; Beller, M. J. Am.
Chem. Soc. 2000, 122, 10289-10297. (b) Do¨bler, C.; Mehltretter, G.;
Beller, M. Angew. Chem., Int. Ed. 1999, 38, 3026-3028.
(7) (a) Sigman, M. S.; Jensen, D. R. Acc. Chem. Res. 2006, 39, 221-
229. (b) Stahl, S. S. Science 2005, 309, 1824-1826. (c) Stahl, S. S.
Angew. Chem., Int. Ed. 2004, 43, 3400-3420. (d) ten Brink, G.-J.;
Arends, I. W. C. E.; Sheldon, R. A. Science 2000, 287, 1636-1639.
10.1021/ic700632f CCC: $37.00
Published on Web 06/13/2007
© 2007 American Chemical Society
Inorganic Chemistry, Vol. 46, No. 14, 2007 5465