Water oxidation at a tetraruthenate core stabilized by polyoxometalate ligands: Experimental and computational evidence to trace the competent intermediates

Journal of the American Chemical Society

Volumn 131, Issue 44, 2009, Pages 16051-16053

  Sartorel, Andrea ^a   Miró, Pere ^b   Salvadori, Enrico ^a   Romain, Sophie ^b   Carraro, Mauro ^a   Scorrano, Gianfranco ^a   Di Valentin, Marilena ^a   Llobet, Antoni ^b   Bo, Carles ^b,c   Bonchio, Marcella ^a  

^a UNIVERSITY OF PADOVA   (Italy)

^b INSTITUTE OF CHEMICAL RESEARCH OF CATALONIA ICIQ   (Spain)

^c UNIVERSITAT ROVIRA I VIRGILI   (Spain)

Author keywords

[No Author keywords available]

Indexed keywords

CATALYTIC CONDITIONS; CATALYTIC CYCLES; CHEMICAL EQUATIONS; DFT CALCULATION; HYDROXO SPECIES; NATURAL ENZYME; NUCLEOPHILIC ATTACK; OXIDATION STATE; POLYOXOMETALATES; WATER MOLECULE; WATER OXIDATION;

OXIDATION; SULFUR COMPOUNDS;

CATALYTIC OXIDATION;

CALCIUM; MANGANESE; TRANSITION ELEMENT;

ARTICLE; CATALYSIS; CHEMICAL STRUCTURE; CYCLIC POTENTIOMETRY; ELECTRON SPIN RESONANCE; OXIDATION; PH MEASUREMENT;

EID: 70450208568     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja905067u     Document Type: Article

References (37)

1. (a) Que, L., Jr; Tolman, W. B. Angew. Chem., Int. Ed. 2002, 41, 1114-1137.
2. (b) Que, L., Jr.; Tolman, W. B. Nature 2008, 455, 333-340.
3. Ferreira, K. N.; Iverson, T. M.; Maghlaoui, K.; Barber, J.; Iwata, S. Science 2004, 303, 1831-1838.
4. (a) Sproviero, E. M.; Gascon, J. A.; McEvoy, J. P.; Brudvig, G. W.; Batista, V. S. Coord. Chem. Rev. 2008, 252, 395-415.
5. (b) Sauer, K.; Yano, J.; Yachandra, V. K. Coord. Chem. Rev. 2008, 252, 318-335.
6. (a) Gray, H. B. Nat. Chem. 2009, 1, 7.
7. (b) Eisenberg, R; Gray, H. B. Inorg. Chem. 2008, 47, 1697-1699.
8. (c) Meyer, T. J. Nature 2008, 451, 778-779.
9. (a) Lutterman, D. A.; Surendranath, Y.; Nocera, D. G. J. Am. Chem. Soc. 2009, 131, 3838-3839.
10. (b) Kanan, M. W.; Nocera, D. G. Science 2008, 321, 1072-1075.
11. (c) McDaniel, N. D.; Coughlin, F. J.; Tinker, L. L.; Bernhard, S. J. Am. Chem. Soc. 2008, 130, 210-217.
12. (d) Tinker, L. L.; McDaniel, N. D.; Bernhard, S. J. Mater. Chem. 2009, 19, 3328-3337.
13. Sala, X.; Romero, I.; Rodríguez, M.; Viñas, C.; Parella, T.; Llobet, A. Angew. Chem., Int. Ed. 2009, 48, 2842-2852.
14. (a) Concepcion, J. J.; Jurss, J. W.; Templeton, J. L.; Meyer, T. J Proc. Natl. Acad. Sci. U.S.A. 2008, 105, 17632-17635.
15. (b) Gersten, S. W.; Samuels, G. J.; Meyer, T. J. J. Am. Chem. Soc. 1982, 104, 4029-4030.
16. Sens, C.; Romero, I.; Rodríguez, M.; Llobet, A.; Parella, T.; Benet-Bucholz, J. J. Am. Chem. Soc. 2004, 126, 7798-7799.
17. Sartorel, A.; Carraro, M.; Scorrano, G.; De Zorzi, R.; Geremia, S.; McDaniel, N. D.; Bernhard, S.; Bonchio, M. J. Am. Chem. Soc. 2008, 130, 5006-5007.
18. (a) Geletii, Y. V.; Botar, B.; Köegerler, P.; Hillesheim, D. A.; Musaev, D. G.; Hill, C. L. Angew. Chem., Int. Ed. 2008, 47, 3896-3899.
19. (b) Geletii, Y. V.; Huang, Z.; Hou, Y.; Musaev, D. G.; Lian, T.; Hill, C. L. J. Am. Chem. Soc. 2009, 131, 7522-7523.
20. Liu, F.; Concepcion, J. J.; Jurss, J. W.; Cardolaccia, T.; Templeton, J. L.; Meyer, T. J. Inorg. Chem. 2008, 47, 1727-1752.
21. Romero, I.; Rodríguez, M.; Sens, C.; Mola, J.; Kollipara, M. R.; Francas, L.; Mas-Marza, E.; Esriche, L.; Llobet, A. Inorg. Chem. 2008, 47, 1824-1834.
22. Large g anisotropy and 〈g〉 values significantly lower than the free electron value have been observed for paramagnetic intermediates of the ruthenium blue dimer (see ref 15). The sharp component with g = 1.77, although appearing as a prominent feature in the experimental spectrum, represents only a 10% contribution to the overall signal, as estimated by double integration.
23. Lahootun, V.; Besson, C.; Villanneau, R.; Villain, F.; Chamoreau, L.-M.; Boubekeur, K.; Blanchard, S.; Thouvenot, R.; Proust, A. J. Am. Chem. Soc. 2007, 129, 7127-7135.
24. Yamada, H.; Hurst, J. K. J. Am. Chem. Soc. 2000, 122, 5303-5311.
25. 2 vibrations.
26. -1. Calculated energies and geometric parameters reported in the paper refer to the gas phase. Single-point calculations including solvent effects do not show significant changes.
27. a for the Ru(V)-hydroxo group in 2 was calculated by DFT to be 4.2, thus confirming the attribution of a protonated state at pH 0.6; see Supporting Information, Figure S15.
28. -1 more stable than 3a. Note that DFT methods are unable to properly describe open-shell singlet states; see: Ziegler, T.; Rauk, A.; Baerends, E. J. Theor. Chim. Acta 1977, 43, 261-271.
29. The observed, complex line shape could be due to dipolar interactions between different molecules or to partial aggregation or precipitation phenomena at the cryogenic temperature of the experiment.
30. 4 state.
31. -1, depending on the level of theory used; see Tables S1 and S2. In analogy with 3 (see ref 19), two structural isomers 6a and 6b have been considered, with 6b being slightly more stable than 6a.
32. A similar scenario results for the two Ru(VI)-oxo functionalities in 6a (Figure S16), where the LUMO+1 is mostly localized.
33. Romain, S.; Bozoglian, F.; Sala, X.; Llobet, A. J. Am. Chem. Soc. 2009, 131, 2768-2769.
34. 4-core.
35. McEvoy, J. P.; Brudvig, G. V. Chem. Rev. 2006, 106, 4455-4483.
36. 2, has been observed in both acidic and neutral aqueous solutions.
37. Few polynuclear Mn-based complexes have been reported to oxidize water to oxygen with low turnovers, but their activity is still debated, as in most cases peroxides have been used as the oxidant. See: Mullins, C. S.; Pecoraro, V. L. Coord. Chem. Rev. 2008, 252, 416-443.