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Electrocatalytic reduction of protons to hydrogen by a water-compatible cobalt polypyridyl platformw

Julian P. Bigi,ab Tamara E. Hanna,ab W. Hill Harman,ab Alicia Changa and Christopher J. Chang*abc
Received (in Berkeley, CA, USA) 3rd August 2009, Accepted 9th December 2009 First published as an Advance Article on the web 23rd December 2009 DOI: 10.1039/b915846d A cobalt(II) complex supported by the new tetradentate polypyridyl ligand PY4 is an electrocatalyst for the reduction of protons to hydrogen and can operate in 50% aqueous media. Hydrogen derived from non-carbon sources has emerged as a potential fuel for sustainable energy cycles that minimize carbon dioxide emissions.1 As such, the search for catalysts that can facilitate the reduction of protons to hydrogen using cheap and earth-abundant metals is an area of current interest.2,3 However, despite recent advances in the eld, creating catalysts that generate hydrogen from protons at minimal overpotentials, possess high activity and stability, and operate in benign aqueous media remains an outstanding challenge; as such, no single synthetic system possesses all of these desirable properties.2 Because the major classes of hydrogen-producing small molecules reported to date include metalsulfur clusters related to hydrogenase enzymes,3,4 iron, cobalt, and nickel macrocycles,5 and cobalt and nickel cyclopentadienyl and phosphine complexes,6 we sought to explore alternative supporting ligand scaolds to meet this goal. We now present a new tetradentate polypyridine platform and the ability of its cobalt(II) derivative to reduce protons to hydrogen in acetonitrile solution. This catalyst can also operate in up to 50% aqueous media. We reasoned that pyridine donors could stabilize reducing metal-based species with favorable aqueous compatibility. Inspired by the pentadentate PY5 platform used for biomimetic iron and manganese oxidation chemistry,7 we sought to create tetradentate analogs that would support octahedral metal complexes with two xed cis open coordination sites for reduction chemistry. Scheme 1 outlines the synthesis of 2-bis(2-pyridyl)(methoxy)methyl-6-pyridylpyridine (PY4) based on these considerations.w Lithiation of 2,6-dibromopyridine followed by reaction with 2,2 0 -dipyridylketone aords 1 in 50% yield. Methylation of 1 with iodomethane provides 2 in 52% yield, and subsequent Stille coupling with
a

2-trimethylstannylpyridine with catalytic Pd(PPh3)4 and CuI furnishes the nal ligand PY4 (3) in 64% yield. Metal insertion with CoCl2 followed by salt metathesis with TlPF6 generates the cationic cobalt(II) PY4 complex 4. The X-ray crystal structure of 4 conrms the expected octahedral geometry adopted at Co(II) for this compound (Fig. 1, left). Metalation with ZnCl2 followed by TlPF6 treatment delivers the corresponding Zn(II) PY4 congener 5 as a ve-coordinate complex (Fig. 1, right).z Fig. 2 displays cyclic voltammogram (CV) data of 4 in acetonitrile solution with varying amounts of triuoroacetic acid (TFA). In the absence of acid, the CV of 4 features a reversible reductive wave at 0.81 V vs. SCE; we assign this wave to a metal-centered Co(II)/Co(I) reduction process as both the corresponding Zn(II) PY4 complex 5 and free PY4 ligand are electrochemically silent in this potential range. A quasi-reversible oxidative wave at +0.87 V vs. SCE (DEp = 430 mV) is likely due to the Co(III)/Co(II) couple (Fig. S1, ESIw). The addition of TFA triggers the appearance of a catalytic wave near the Co(II)/Co(I) couple of 4 that plateaus at higher acid concentrations (Fig. 2). Analysis of controlled-potential electrolysis samples conrms the production of hydrogen with a ca. 99% Faraday yield, suggesting that the observed current enhancements are due to electrocatalytic reduction of protons. To determine the order of the electrocatalysis in 4 and TFA, we performed a series of CV measurements under electrocatalytic conditions with a large excess of acid and at suciently negative potentials that electron transfer is fast. Under these conditions, for a reaction rst-order in catalyst and second-order in acid, the plateau current (ic) is related to

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Department of Chemistry, University of California, Berkeley, CA 94720, USA b Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USA. E-mail: chrischang@berkeley.edu; Fax: +1 5106427301; Tel: +1 5106434704 c Howard Hughes Medical Institute, University of California, Berkeley, CA 94720, USA w Electronic supplementary information (ESI) available: Procedures for synthetic, spectroscopic, and electrochemical experiments. CCDC 743197 and 743198. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/b915846d

Scheme 1

Synthesis of PY4 and its Co(II) and Zn(II) complexes.

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Fig. 1 Solid-state structures of complexes 4 (left) and 5 (right). Anions, solvent molecules and hydrogen atoms are omitted for clarity; thermal ellipsoids are shown at 50% probability.

Fig. 3 Plot of the slopes from Fig. S3 (ESIw) vs. n1/2. The linear t is 1.295x + 0.626, R = 0.9992. The rate constant for hydrogen production, k, can be calculated from the slope to be ca. 3 M2 s1. For 60 mM TFA, this corresponds to a turnover frequency (TOF) of ca. 40 mol H2/(mol 4 h).

Fig. 2 Cyclic voltammograms of complex 4 in 0.1 M Bu4NPF6 in acetonitrile in the presence of triuoroacetic acid (TFA): (bottomtop) 1.0 mM 4 with no acid, 5.2 mM TFA, 10.4 mM TFA, 15.6 mM TFA, and 26.0 mM TFA. Scan rate: 100 mV s1; glassy carbon electrode.

the concentrations of catalyst and acid by the following expression:8 q ic nFAcat DkH 2 Plotting the plateau current as a function of the concentration of 4 reveals that hydrogen generation is rst-order in 4 (Fig. S2, ESIw). An analogous plot of ic as a function of [TFA] shows that the process is second-order in TFA (Fig. S3, ESIw). With this information, according to the following equation, plotting ic/ip vs. [TFA] (Fig. S4, ESIw) should be linear for dierent scan rates (where ip is the peak current in the absence of acid).6c,8 s ic n RTkH 2 ip 0:4463 Fv The turnover frequency (TOF) calculated by plotting the slopes of these lines against n1/2 is ca. 40 mol H2/(mol 4 h) for [TFA] E 60 mM, a concentration of acid compatible with 4 (Fig. 3), with H2 production occurring at an overpotential of ca. 400 mV.9 Notably, the Zn(II) PY4 complex 5 does not catalyze hydrogen production under these conditions, implicating the need for a redox-active metal center for electrocatalysis (Fig. S5, ESIw). The observation that the electrocatalytic current for hydrogen production occurs near the Co(II)/Co(I) couple for 4 suggests that a reduced Co(I) species is involved in the
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catalytic cycle. We monitored spectral changes for this Co(II)/Co(I) reduction process by UV-visible absorption spectroelectrochemistry using an optically semi-transparent thin layer electrode (OSTTLE). As shown in Fig. S6 (ESIw), the reversible electrochemical reduction of 4 results in the appearance of two new features in the electronic absorption spectrum, a broad band at 550 nm with a shoulder near 600 nm and a weaker absorption centered at 900 nm. So far, we have been unable to obtain X-ray quality crystals of the reduced Co(I) species. Finally, we sought to test whether electrocatalytic proton reduction mediated by 4 is compatible with aqueous conditions. The compound is suciently soluble to obtain reproducible electrochemical behavior in 1 : 1 wateracetonitrile solution but is not soluble in pure aqueous media at millimolar concentrations. The CV of 4 in 1 : 1 wateracetonitrile solution shows a reversible Co(II)/Co(I) reduction wave in the absence of acid (Fig. 4). The addition of TFA triggers an electrocatalytic current near the Co(II)/Co(I) couple consistent with hydrogen production, as observed for reactions in acetonitrile. In closing, we have presented a new polypyridyl platform and the ability of its octahedral cobalt(II) derivative to

Fig. 4 Cyclic voltammograms of complex 4 in 0.1 M KNO3 in 1 : 1 wateracetonitrile in the presence of TFA: (bottomtop) 1.0 mM 4 with no acid, 1.3 mM TFA, 2.6 mM TFA, 3.9 mM TFA, and 5.2 mM TFA. Scan rate: 100 mV s1; glassy carbon electrode.

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electrocatalytically reduce protons to hydrogen. The collective data suggest involvement of a Co(I) species and show that proton reduction is compatible in media containing up to 50% water. Ongoing and future work is geared toward additional mechanistic studies as well as exploiting the tunability of PY4 and related platforms to create catalysts with improved activity, reduced overpotentials, and compatibility with pure aqueous media. This work was funded by the Helios Solar Energy Research Center (51HE112B), which is supported by the Director, Oce of Science, Oce of Basic Energy Sciences of the U.S. Department of Energy under Contract No. DE-AC0205CH11231. We also thank the University of California, Berkeley, the Dreyfus, Beckman, Packard, and Sloan Foundations, and the LBNL Chemical Sciences Division (403801) for research support. J.P.B. and W.H.H. were also supported by graduate fellowships from NSF and Arkema, respectively. We thank Dr Deanna DAlessandro and Prof Je Long for help with spectroelectrochemistry, Ms Melissa Fardy and Prof Peidong Yang for use of their gas chromatography instrument, and Dr Antonio DiPasquale and Dr Frederick J. Hollander for assistance with crystallography.

Notes and references

) radiation. 4: z Crystal data for 4 and 5 with Mo-Ka (l = 0.71073 A C30H32CoF12N6O2P2, FW = 857.49, T = 136 K, monoclinic, space , group P21/c; a = 11.9665(12), b = 11.8487(12), c = 25.024(2) A 3, R = 0.052 for 5360 b = 90.723(2)1, Z = 4, V = 3547.8(6) A (I > 2s(I)), Rint = 0.039, 19 864 reections measured, CCDC no. 743197. 5: C24H21F12N5OP2Zn, FW = 750.77, T = 143 K, monoclinic, space group P21/n; a = 14.0273(77), b = 13.6709(75), 3, R = 0.064 c = 16.2887(89), b = 110.767(6)1, Z = 4, V = 2921(3) A for 3533 (I > 2s(I)), Rint = 0.032, 11 717 reections measured, CCDC no. 743198. 1 (a) J. A. Turner, Science, 2004, 305, 972974; (b) N. S. Lewis and D. G. Nocera, Proc. Natl. Acad. Sci. U. S. A., 2006, 103, 1572915735. 2 (a) J. W. Peters, W. N. Lanzilotta, B. J. Lemon and L. C. Seefeldt, Science, 1998, 282, 18531858; (b) E. Garcin, X. Vernede, E. C. Hatchikian, A. Volbeda, M. Frey and J. C. Fontecilla-Camps, Structure, 1999, 7, 557566; (c) M. Frey, ChemBioChem, 2002, 3, 153160; (d) F. A. Armstrong, Curr. Opin. Chem. Biol., 2004, 8, 133140; (e) S. Shima, O. Pilak, S. Vogt, M. Schick, M. S. Stagni, W. Meyer-Klaucke, E. Warkentin, R. K. Thauer and U. Ermler, Science, 2008, 321, 572575. 3 (a) U. Koelle, New J. Chem., 1992, 16, 157169; (b) M. Y. Darensbourg, E. J. Lyon, X. Zhao and I. P. Georgakaki, Proc. Natl. Acad. Sci. U. S. A., 2003, 100, 36833688; (c) D. J. Evans and C. J. Pickett, Chem. Soc. Rev., kermark and S. Ott, Coord. 2003, 32, 268275; (d) L. Sun, B. A Chem. Rev., 2005, 249, 16531663; (e) A. J. Esswein and D. G. Nocera, Chem. Rev., 2007, 107, 40224047; (f) S. Canaguier, V. Artero and M. Fontecave, Dalton Trans., 2008, 315325; (g) M. R. DuBois and D. L. DuBois, Chem. Soc. Rev., 2009, 38, 6272; (h) F. Gloaguen and T. B. Rauchfuss, Chem. Soc. Rev., 2009, 38, 100108; (i) For a double issue on hydrogenases, see: Coord. Chem. Rev., 2005, 249, 15171690. 4 (a) F. Gloaguen, J. D. Lawrence and T. B. Rauchfuss, J. Am. Chem. Soc., 2001, 123, 94769477; (b) R. Mejia-Rodriguez, D. Chong, J. H. Reibenspies, M. P. Soriaga and M. Y. Darensbourg, J. Am. Chem. Soc., 2004, 126, 1200412014; (c) S. Ott, M. Kritikos, kermark, L. Sun and R. Lomoth, Angew. Chem., Int. Ed., B. A 2004, 43, 10061009; (d) A. M. Appel, D. L. DuBois and

M. R. DuBois, J. Am. Chem. Soc., 2005, 127, 1271712726; (e) C. Tard, X. Liu, S. K. Ibrahim, M. Bruschi, L. De Gioia, S. C. Davies, X. Yang, L. S. Wang, G. Sawers and C. J. Pickett, Nature, 2005, 433, 610613; (f) B. Keita, S. Floquet, J. F. Lemonnier, E. Cadot, A. Kachmar, M. Benard, M. M. Rohmer and L. Nadjo, J. Phys. Chem. C, 2008, 112, 11091114; (g) G. A. N. Felton, A. K. Vannucci, J. Chen, L. T. Lockett, N. Okumura, B. J. Petro, U. I. Zakai, D. H. Evans, R. S. Glass and D. L. Lichtenberger, J. Am. Chem. Soc., 2007, 129, 1252112530; (h) S. Ogo, R. Kabe, K. Uehara, B. Kure, T. Nishimura, S. C. Menon, R. Harada, S. Fukuzumi, Y. Higuchi, T. Ohhara, T. Tamada and R. Kuroki, Science, 2007, 316, 585587; (i) P. Li, M. Wang, J. Pan, L. Chen, N. Wang and L. Sun, J. Inorg. Biochem., 2008, 102, 952959. (a) B. J. Fisher and R. Eisenberg, J. Am. Chem. Soc., 1980, 102, 73617363; (b) R. M. Kellett and T. G. Spiro, Inorg. Chem., 1985, 24, 23732377; (c) R. M. Kellett and T. G. Spiro, Inorg. Chem., 1985, 24, 23782382; (d) A. Bakac, M. E. Brynildson and J. H. Espenson, Inorg. Chem., 1986, 25, 41084114; (e) P. Connolly and J. H. Espenson, Inorg. Chem., 1986, 25, 26842688; (f) J. P. Collin, A. Jouaiti and J. P. Sauvage, Inorg. Chem., 1988, 27, 19861990; (g) I. Bhugun, D. Lexa and ant, J. Am. Chem. Soc., 1996, 118, 39823983; J. M. Save (h) T. L. James, L. Cai, M. C. Muetterties and R. H. Holm, Inorg. Chem., 1996, 35, 41484161; (i) R. Abdel-Hamid, H. M. El-Sagher, A. M. Abdel-Mawgoud and A. Nafady, Polyhedron, 1998, 17, 45354541; (j) P. V. Bernhardt and L. A. Jones, Inorg. Chem., 1999, 38, 50865090; (k) X. Hu, B. M. Cossairt, B. S. Brunschwig, N. S. Lewis and J. C. Peters, Chem. Commun., 2005, 47234725; (l) M. Razavet, V. Artero and M. Fontecave, Inorg. Chem., 2005, 44, 47864795; (m) C. Baert, V. Artero and M. Fontecave, Inorg. Chem., 2007, 46, 18171824; (n) X. Hu, B. S. Brunschwig and J. C. Peters, J. Am. Chem. Soc., 2007, 129, 89888998; (o) A. Fihri, V. Artero, M. Razavet, C. Baert, W. Leibl and M. Fontecave, Angew. Chem., Int. Ed., 2008, 47, 564567; (p) P. Du, K. Knowles and R. Eisenberg, J. Am. Chem. Soc., 2008, 130, 1257612577; (q) O. Pantani, S. Naskar, R. Guillot, M. Millet, E. Anxolabehere-Mallart and A. Aukauloo, Angew. Chem., Int. Ed., 2008, 47, 99489950. (a) V. Houlding, T. Geiger, U. Koelle and M. Graetzel, J. Chem. Soc., Chem. Commun., 1982, 681683; (b) U. Koelle and S. Paul, Inorg. Chem., 1986, 25, 26892694; (c) U. Koelle, P. P. Infelta and M. Graetzel, Inorg. Chem., 1988, 27, 879883; (d) A. D. Wilson, R. H. Newell, M. J. McNevin, J. T. Muckerman, M. R. DuBois and D. L. DuBois, J. Am. Chem. Soc., 2006, 128, 358366. (a) R. T. Jonas and T. D. P. Stack, J. Am. Chem. Soc., 1997, 119, 85668567; (b) M. E. Vries, R. M. L. Crois, G. Roelfes, H. Kooijman, A. L. Spek, R. Hage and B. L. Feringa, Chem. Commun., 1997, 15491550; (c) C. R. Goldsmith, R. T. Jonas, A. P. Cole and T. D. P. Stack, Inorg. Chem., 2002, 41, 46424652; (d) C. R. Goldsmith, R. T. Jonas and T. D. P. Stack, J. Am. Chem. Soc., 2002, 124, 8396; (e) R. J. M. Klein Gebbink, R. T. Jonas, C. R. Goldsmith and T. D. P. Stack, Inorg. Chem., 2002, 41, 46334641; (f) G. Roelfes, V. Vrajmasu, K. Chen, R. Y. N. Ho, J. U. Rohde, C. Zondervan, R. M. la Crois, E. P. Schudde, M. Lutz, A. L. Spek, R. Hage, B. L. Feringa, E. Mu nck and L. Que, Jr., Inorg. Chem., 2003, 42, 26392653; (g) C. R. Goldsmith, A. P. Cole and T. D. P. Stack, J. Am. Chem. Soc., 2005, 127, 99049912; (h) C. R. Goldsmith and T. D. P. Stack, Inorg. Chem., 2006, 45, 60486055. (a) A. J. Bard and L. R. Faulkner, in Electrochemical Methods: Fundamentals and Applications, John Wiley & Sons, Inc., New York, 2nd edn, 2001; (b) C. P. Andrieux, C. Blocman, ant, J. Electroanal. J. M. Dumasbouchiat, F. Mhalla and J. M. Save Chem., 1980, 113, 1940; (c) P. Delahay and G. L. Stiehl, J. Am. Chem. Soc., 1952, 74, 35003505; (d) R. S. Nicholson and I. Shain, ant and E. Vianello, Anal. Chem., 1964, 36, 706723; (e) J. M. Save ant and Electrochim. Acta, 1965, 10, 905920; (f) J. M. Save E. Vianello, Electrochim. Acta, 1967, 12, 629646. G. A. N. Felton, R. S. Glass, D. L. Lichtenberger and D. H. Evans, Inorg. Chem., 2006, 45, 91819184.

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