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Electrochemical evidence for catalytic water oxidation mediated by a high-valent cobalt complexw
Downloaded by Ewha Womens University on 27 March 2013 Published on 28 February 2011 on http://pubs.rsc.org | doi:10.1039/C0CC05522K

Derek J. Wasylenko, Chelladurai Ganesamoorthy, Javier Borau-Garcia and Curtis P. Berlinguette*

Received 12th December 2010, Accepted 8th February 2011 DOI: 10.1039/c0cc05522k The pH-dependent electrochemical behavior for a Co(II) complex, [Co(Py5)(OH2)](ClO4)2 (1; Py5 = 2,6-(bis(bis-2-pyridyl)methoxymethane)pyridine), indicates consecutive (proton-coupled) oxidation steps furnish a CoIV species that catalyzes the oxidation of water in basic media. Reactions that involve the simultaneous transfer of protons and electrons enable the build-up of the redox equivalents necessary for multi-electron transformations that bypass high-energy intermediates.1,2 Consequently, proton-coupled electron-transfer (PCET) is a critical aspect of many important energy conversion processes in biology and chemistry.36 A complete mechanistic understanding of PCET is particularly relevant to the long-standing goal of eciently separating water into its constituents as a means of storing solar energy.1,4,5,7 Among the recent breakthroughs in the broad area of water oxidation catalysis is the recognition that synthetic complexes containing a single Ru or Ir site can mediate the multiple proton and electron-transfer events associated with water oxidation (Fig. 1).814 Importantly, these well-dened and relatively robust catalysts have enabled a detailed mechanistic account of the complicated reaction landscape.9,15,16 Key features that emerge from these studies include the identication that: (i) PCET stabilizes the overall charge of the catalysts to render a high-valent [MQO]z unit accessible; and (ii) the critical OO bond-forming step involves the nucleophilic attack of water at said [MQO]z site (e.g. [RuVQO]3+,9,16 [RuIVQO]2+,16 or [IrVQO]3+;15 (Fig. 1). Given the limited precedent for single-site catalysts containing rst-row transition metals,17 and the recent advancements in polynuclear18 and heterogeneous4,1921 Co-based catalysts, we set out to establish whether a high-valent Co molecular fragment could be established in an aqueous medium, and, if so, investigate its reactivity towards water.22 Despite the extensive PCET studies on polypyridyl complexes of second- and third-row transition-metal (TM) aqua complexes,1,2,23 to our knowledge there is no documented example of a tetravalent Co centre stabilized by PCET in an analogous fashion.24 One of the challenges in accessing this redox level is nding an appropriate oxidatively stable coordination environment.10 While more than one chelating ligand can be used to stabilize Ru and Ir aqua/hydroxy/oxo complexes (e.g. 2,2 0 -bipyridine and Cp*; Fig. 1), the facile preparation of stable Co analogues is hampered by the inherent lability of the divalent Co centre. Moreover, the metalligand bond opposite to the MO bond can be compromised at higher redox levels making the catalyst susceptible to degradation.10 In order to overcome these obstacles, we utilized the oxidatively stable pentadentate ligand environment of 2,6-(bis(bis-2-pyridyl)methoxy-methane)pyridine (Py5) to form the stable coordination compound, [Co(Py5)(OH2)](ClO4)2 (1; Fig. 2). Herein, we show that this complex undergoes a PCET step to stabilize a [CoIIIOH]2+ unit, and that the further oxidation of this complex renders a Co(IV) species that reacts with water in the presence of a base. The Py5 ligand was rst developed independently and concurrently by Stack et al.25 and Feringa et al.26 While the versatility of Py5 in forming rst-row TM complexes has already been established,27,28 we considered it to be a candidate for withstanding the harshly oxidizing conditions necessary for oxidizing water because the local ligand environment about the metal is oxidatively stable and not susceptible to undesirable b-H elimination processes. The pentadentate chelate also leaves a coordination site available for the ligation of the water substrate about the pseudo-octahedral Co(II) centre, while also preserving the CoN bond trans to the O atom during catalysis. Thus, we

Department of Chemistry, University of Calgary and the Institute for Sustainable Energy, Environment & Economy, University of Calgary, 2500 University Drive N.W., Calgary, Canada T2N-1N4. E-mail: cberling@ucalgary.ca; Tel: +1-403-220-3856 w Electronic supplementary information (ESI) available: Synthesis and characterization details, dioxygen formation traces, DFT and crystallographic data. CCDC 804604. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c0cc05522k

Fig. 1 The structural motifs of the catalytically active forms of select single-site9,16 and Co-based4,1821 water oxidation catalysts.

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Fig. 2 A structural representation of [CoII(Py5)(OH2)](ClO4)2 (1). (Relevant metrics are provided in the ESIw).

prepared the aqua complex 1 by treating the ligand with [Co(H2O)6](ClO4)2. The product is formed in high yield and purity; details are provided in the ESIw. The single-crystal X-ray structure determination of the complex reveals metrical ) parameters (e.g. average CoN bond distances of ca. 2.16 A that are consistent with a high-spin Co(II) ion (Table S1w). This assignment is corroborated by spectroscopic (Fig. S2w) and electrochemical (vide infra) data. The cyclic voltammogram of 1 in a buered aqueous solution shows a single reversible metal-based oxidation process at +0.75 V vs. NHE at pH 2.2. This redox couple exhibits a pH dependence of ca. 59 mV per pH decade up to ca. pH 11.7 (Fig. 3); thus, we assign this pH dependent process as a PCET step corresponding to the [CoIIIOH]2+/[CoIIOH2]2+ couple. To our knowledge, this is the rst evidence of a single-site Co complex undergoing PCET where proton-transfer occurs exclusively at the aqua/hydroxy ligand. A second oxidation process is evident at ca. +1.4 V vs. NHE over the pH range 7.610.3 (data recorded at pH 9.2 is provided in Fig. 4). This redox process generates a signicant rise in the current consistent with a catalytic process. The Co-based oxidation event is assigned as the formation of a [CoIVOH]3+ species, where the E1/2 value for the [CoIVOH]3+/[CoIIIOH]2+ couple is estimated by squarewave voltammetry to be +1.43 V vs. NHE. This step is not classied as a PCET event on the basis that the E1/2 value is static over this pH range. While this particular signal is not observed at lower pH values, a distinctive pH dependence is observed at pH > 10.3 (i.e. DE B 59 mV/pH decade) consistent with the PCET step [CoIV]O]2+/[CoIIIOH]2+. Note that the slope corresponding to the purported PCET process at pH > 10.3 is oset from the [CoIVOH]3+/[CoIIIOH]2+ trend line over the pH range 7.610.3 . This curious behavior may be manifest in the interaction between the base and the [CoIVOH]3+ species; however, we dont exclude the possible

Fig. 3 Pourbaix diagram for 1.

formation of a Co oxide decomposition product under these strongly basic conditions (i.e. pH > 10.3). The catalytic oxidation of water over the pH range 7.610.3 (i.e. where catalyst decomposition does not occur) is indicated by the substantial increase in current (I) at ca. E > +1.2 V vs. NHE relative to the Co(III)/Co(II) PCET step (Fig. 4). This catalytic process2 occurs with an overpotential (Z) of ca. 0.5 V (e.g. E1 (H2O/O2) = +0.69 V vs. NHE at pH 9.2), which appears to be one of the lowest values reported for a synthetic catalyst.7 A series of control experiments exclude the catalytic wave being a result of auxiliary chemical processes. For example, various reference electrodes and ultrapure Millipore water were employed to exclude adventitious Cl ions. The possibility of a catalytically active Co oxide lm generated by the decomposition of the complex was ruled out below pH 10.3 by using freshly polished electrodes and successive cycling experiments. The electrochemical behavior of the title complex is clearly distinguished from the prolic CoPi lms by a slightly dierent onset voltage for catalysis and the lack of an anodic wave at Ep,a = +1.13 V (Fig. S3w).19,29 While the electrodes show no evidence of a deposited lm below pH 10.3 (Fig. S4w), some lm deposition was observed in more strongly basic media. Based on these collective observations, the rise in current at B+1.4 V over the pH range 7.610.3 is attributed to the oxidation of water catalyzed by 1. A uorescence optical probe immersed in the solution conrmed dioxygen evolution at an applied potential of +1.59 V vs. NHE over 10 mins (Fig. S5w).30 The catalytic current increases as the scan rate (v) decreases, indicating that the rate-determining step is a chemical process (e.g. OO bond formation) and experiments suggest a reaction rate coecient (kcat) of B79 s1.31,32 This value appears to be higher than that observed for any other molecular catalyst reported to date.7 Given that dioxygen formation with documented single-site Ru and Ir catalysts involves an electrophilic MQO unit, the attack of water at the [CoIVOH]3+ species may require an intermediary. We postulate that a base (e.g. OH, phosphate) assists OO bond formation in a concerted bond reorganization process, or by deprotonating the hydroxide complex to stabilize the [CoIV]O]2+ motif. Both scenarios involve the nucleophilic attack of the Co-hydroxy/oxo species by an incoming water/hydroxide substrate to generate a Coperoxido complex. The catalytic wave observed with the second oxidation event at pH > 10.2 provides some testimony to the [CoIV]O]2+ form being the catalytically active species; however, we cannot conclusively rule out a deposited lm being the source of the catalysis under these strongly basic conditions. Supporting evidence for the critical role of base in these reactions is provided by the absence of the catalytic peak current in acidic media. We note there is precedent for base-assisted OO bond formation with Ru33 and Ir15 catalysts. The reactivity of the CoO motif towards water is corroborated by the orbital character of a low-lying LUMO + 1 CoIV]OH s* orbital that is poised for nucleophilic attack (Fig. 5), which parallels the puportedly active forms of higher nuclearity Co catalysts.18,21,29 This report describes the rst synthetic water oxidation catalyst containing a single Co centre that exhibits remarkably
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4 T. A. Betley, Q. Wu, T. Van Voorhis and D. G. Nocera, Inorg. Chem., 2008, 47, 18491861. 5 L. Hammarstrom and S. Hammes-Schier, Acc. Chem. Res., 2009, 42, 18591860. 6 J. Stubbe, D. G. Nocera, C. S. Yee and M. C. Y. Chang, Chem. Rev., 2003, 103, 21672201. 7 T. R. Cook, D. K. Dogutan, S. Y. Reece, Y. Surendranath, T. S. Teets and D. G. Nocera, Chem. Rev., 2010, 110, 64746502. 8 J. J. Concepcion, J. W. Jurss, M. K. Brennaman, P. G. Hoertz, A. O. T. Patrocinio, N. Y. Murakami Iha, J. L. Templeton and T. J. Meyer, Acc. Chem. Res., 2009, 42, 19541965. 9 J. J. Concepcion, J. W. Jurss, J. L. Templeton and T. J. Meyer, J. Am. Chem. Soc., 2008, 130, 1646216463. 10 D. J. Wasylenko, C. Ganesamoorthy, B. D. Koivisto, M. A. Henderson and C. P. Berlinguette, Inorg. Chem., 2010, 49, 22022209. 11 S. Masaoka and K. Sakai, Chem. Lett., 2009, 38, 182183. 12 L. L. Duan, A. Fischer, Y. H. Xu and L. C. Sun, J. Am. Chem. Soc., 2009, 131, 1039710399. 13 N. D. McDaniel, F. J. Coughlin, L. L. Tinker and S. Bernhard, J. Am. Chem. Soc., 2008, 130, 210217. 14 J. F. Hull, D. Balcells, J. D. Blakemore, C. D. Incarvito, O. Eisenstein, G. W. Brudvig and R. H. Crabtree, J. Am. Chem. Soc., 2009, 131, 87308731. 15 J. D. Blakemore, N. D. Schley, D. Balcells, J. F. Hull, G. W. Olack, C. D. Incarvito, O. Eisenstein, G. W. Brudvig and R. H. Crabtree, J. Am. Chem. Soc., 2010, 132, 1601716029. 16 D. J. Wasylenko, M. A. Henderson, C. Ganesamoorthy, B. D. Koivisto, H. G. Ostho and C. P. Berlinguette, J. Am. Chem. Soc., 2010, 132, 1609416106. 17 W. C. Ellis, N. D. McDaniel, S. Bernhard and T. J. Collins, J. Am. Chem. Soc., 2010, 132, 1099010991. 18 Q. Yin, J. M. Tan, C. Besson, Y. V. Geletii, D. G. Musaev, A. E. Kuznetsov, Z. Luo, K. I. Hardcastle and C. L. Hill, Science, 2010, 328, 342345. 19 Y. Surendranath, M. W. Kanan and D. G. Nocera, J. Am. Chem. Soc., 2010, 132, 1650116509. 20 D. K. Zhong and D. R. Gamelin, J. Am. Chem. Soc., 2010, 132, 42024207. 21 F. Jiao and H. Frei, Angew. Chem., Int. Ed., 2009, 48, 18411844. 22 Note that the so-called oxo-wall prohibits the formation of a formal CoQO double bond; a consequence of the electronicrepulsion between the 5d electrons and the p electrons of the O2 ligand. 23 C. Costentin, M. Robert, J.-M. Saveant and A.-L. Teillout, Proc. Natl. Acad. Sci. U. S. A., 2009, 106, 1182911836, S11829/11821S11829/11825. 24 PCET was invoked for an undened homogeneous cobalt-oxide system: B. S. Brunschwig, M. H. Chou, C. Creutz, P. Ghosh and N. Sutin, J. Am. Chem. Soc., 1983, 105, 48324833. 25 R. T. Jonas and T. D. P. Stack, J. Am. Chem. Soc., 1997, 119, 85668567. 26 M. E. de Vries, R. M. La Crois, G. Roelfes, H. Kooijman, A. L. Spek, R. Hage and B. L. Feringa, Chem. Commun., 1997, 15491550. 27 R. J. M. Klein Gebbink, R. T. Jonas, C. R. Goldsmith and T. D. P. Stack, Inorg. Chem., 2002, 41, 46334641. 28 Note that a related Py5 ligand serves as the foundation for a Mo-based water reduction catalyst: H. I. Karunadasa, C. J. Chang and J. R. Long, Nature, 2010, 464, 1329. 29 M. W. Kanan and D. G. Nocera, Science, 2008, 321, 10721075. 30 Reductive cyclic voltammetric scans conrmed the generation of dioxygen in solution; H2O2 was not detected. 31 P. Zanello, Inorganic Electrochemistry: Theory, Practice and Application, The Royal Society for Chemistry, Cambridge, UK, 2003. 32 kcat at 25 1C was determined from (see Ref. 31): Icat/Idi = 0.323[(kcat/(anav)]1/2, where Icat = catalytic current; Idi = diusional current; a = 0.5; na = 4. 33 Z. Chen, J. J. Concepcion, X. Hu, W. Yang, P. G. Hoertz and T. J. Meyer, Proc. Natl. Acad. Sci. U. S. A., 2010, 107, 72257229.

Downloaded by Ewha Womens University on 27 March 2013 Published on 28 February 2011 on http://pubs.rsc.org | doi:10.1039/C0CC05522K

Fig. 4 A cyclic voltammogram of 1 recorded at pH 9.2 (red line; buer is 0.1 M phosphate; scan rate = 50 mV s1). A blank scan recorded under the same conditions without the catalyst is also provided (black line).

Fig. 5 The orbital character of the s* molecular orbital (LUMO + 1) calculated for [CoIV(Py5)OH]3+.

high activity. In mildly to strongly basic media, the catalytic cycle involves 1 undergoing a well-dened PCET step to furnish [CoIIIOH]2+. This species can then undergo a second oxidation event to form a [CoIVOH]3+ species. The presence of a base serves to enable the reactivity of this high-valent complex towards water to facilitate the OO bond formation process. Using the well-dened reactivity of single-site Ru catalysts as a guide,9,16 subsequent electron-transfer and deprotonation steps presumably furnish a [CoIVOO]2+ complex. The exclusion of dioxygen from this species and the subsequent substrate binding replenishes 1 to close the catalytic cycle. A notable dierence in the reactivity of the Ru and Ir single-site catalysts is that 1 appears to require a base to negotiate the requisite OO bond formation step. Studies are under way to further unravel this mechanistic behavior and exploit the apparently low overpotential and high activity of the catalyst to help reconcile the reactivity with the growing body of literature on polynuclear18 and heterogeneous4,1921 Co-based water oxidation catalysts. Future work will also examine the catalytic activity of other rst-row TMs within this stable ligand framework.

Notes and references

1 M. H. V. Huynh and T. J. Meyer, Chem. Rev., 2007, 107, 50045064. 2 C. Costentin, M. Robert and J.-M. Saveant, Acc. Chem. Res., 2010, 43, 10191029. 3 J. P. Collman, P. S. Wagenknecht and J. E. Hutchison, Angew. Chem., Int. Ed., 1994, 106, 16201639.

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