Inorganic Chemistry
Article
studies.10 Surprisingly, the CV of the Ruphot−Rucat−OH2
complex recorded in our laboratory in the same conditions
(at pH 4.4; acetate buffer) showed significant differences with
the one published (Figure S13, Supporting Information).10
While two waves were observed at +0.75 and +1.2 V vs NHE
and attributed to successive one-electron oxidation processes
Ru(II)−OH2 → Ru(III)−OH → Ru(IV)O, a single wave at
+1.05 V vs NHE corresponding to a two-electron oxidation
process was observed in our case. Our data (CV, RDE, and E-
pH experiments) strongly support a two-electron two proton
process, unambiguously attributed to oxidation of the
Rucat(II)−OH2 fragment into a Rucat(IV)O fragment, as
Chem. Soc. Rev. 2001, 30, 36. (i) De Cola, L.; Belser, P. Coord. Chem.
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also observed for the [Ru(tpy)(bpym)OH2]2+ (Rucat
−
OH2),13,19a,24 [(bpy)Ru(iPrPybox)OH2]2+,25 and trans-[Ru(II)-
26
pyrpy-O)(tpy)−OH2]+ complexes (iPrPybox = 2,6-bis[4-
isopropyl-2-oxazolin-2-yl]pyridine; pyrpy = 3,5-dimethyl-2-(2-
pyridyl)pyrrolate).
Then, similar to the proposed mechanism for water
oxidation, the Ru(IV)O species undergoes nucleophilic
attack of the sulfide to give the corresponding sulfoxide as a
product with regeneration of the ruthenium aquo catalyst. Such
a mechanism was also proposed during dimethylsulfide
oxidation by [(bpy)2Ru(py)O]2+.27 This mechanism was
also suggested by the effect of the substituents on the phenyl
ring of the sulfide with regard to the reactivity (Table 3) even
though each substrate has a different solubility in the aqueous
environment. However, as expected, the more electron
donating the aryl substituent the more efficient the reaction.
In conclusion, we report herein the synthesis of a ruthenium-
based photocatalyst for sulfide photooxygenation. Similar to the
first dyad system reported recently by our group,8a it was
shown that combination of a light-absorbing photosensitizing
fragment and a catalytic subunit within the same entity affords a
better catalytic activity compared to the bimolecular system.
This emphasizes a more efficient synergistic effect between
both partners in the dyad. This finding should represent an
important consideration in the design of future catalysts for
various oxygenation reactions.
̂
J. M.-N; Deronzier, A.; Laguitton-Pasquier, H.; Lepretre, J.-C.; Vial, J.-
C.; Brasme, B. Phys. Chem. Chem. Phys. 2003, 5, 2520 . For
photocatalytic water oxidation, see ref 5. For photocatalytic oxidation
of organic substrates, see refs 7 and 8 .
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ASSOCIATED CONTENT
* Supporting Information
■
S
Actinometry experiment, NMR spectrum of the catalyst,
electronic absorption spectra of the complexes, electrochemical
studies, and photocatalytic oxygenation results. This material is
́ ́
(f) Chavarot, M.; Menage, C; Hamelin, O.; Charnay, F.; Pecaut, J.;
Fontecave, M. Inorg. Chem. 2003, 42, 4810. (g) Goldstein, A. S.;
Drago, R. S. J. Chem. Soc., Chem. Commun. 1991, 21. (h) Hamelin, O.;
́ ́
Menage, S.; Charnay, F.; Chavarot, M.; Pierre, J.-L.; Pecaut, J.;
AUTHOR INFORMATION
Corresponding Author
■
Fontecave, M. Inorg. Chem. 2008, 47, 6413. (i) Meyer, T. J.; Huynh,
M. H. V. Inorg. Chem. 2003, 42, 8140 and references therein.
(j) Benet-Buchholz, J.; Comba, P.; Llobet, A.; Roeser, S.; Vadivelu, P.;
Wadepohl, H.; Wiesner, S. Dalton Trans. 2009, 5910. (k) Benet-
Buchholz, J.; Comba, P.; Llobet, A.; Roeser, S.; Vadivelu, P.;
Wadepohl, H.; Wiesner, S. Dalton Trans. 2010, 39, 3315. (l) Hirai,
Y.; Kojima, T.; Mizutani, Y.; Shiota, Y.; Yoshizawa, K.; Fukuzumi, S.
Angew. Chem., Int. Ed. 2008, 47, 5772. (m) Huynh, M. 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.
ACKNOWLEDGMENTS
Financial support from the CNRS, MENRT, Universite
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́
Bordeaux I, Reg
́
ion Aquitaine is gratefully acknowledged.
REFERENCES
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dx.doi.org/10.1021/ic2022159 | Inorg. Chem. 2012, 51, 2222−2230