Molecular catalysts that oxidize water to dioxygen.

During the past four years we have witnessed a revolution in the field of water-oxidation catalysis, in which well-defined molecules are opening up entirely new possibilities for the design of more rugged and efficient catalysts. This revolution has been stimulated by two factors: the urgent need for clean and renewable fuel and the intrinsic human desire to mimic nature's reactions, in this case the oxygen-evolving complex (OEC) of the photosystem II (PSII). Herein we give a short general overview of the established basis for the oxidation of water to dioxygen as well as presenting the new developments in the field. Furthermore, we describe the new avenues these developments are opening up with regard to catalyst design and performance, together with the new questions they pose, especially from a mechanistic perspective. Finally the challenges the field is facing are also discussed.

[1]  B. Moyer,et al.  Proton-coupled electron transfer between [Ru(bpy)2(py)OH2]2+ and [Ru(bpy)2(py)O]2+. A solvent isotope effect (kH2O/kD2O) of 16.1 , 1981 .

[2]  M. Grabolle,et al.  Photosynthetic O2 Formation Tracked by Time-Resolved X-ray Experiments , 2005, Science.

[3]  M. Kaneko,et al.  Catalytic activity of [(bpy)2(H2O)Ru–O–Ru(H2O)(bpy)2]4+ for four-electron water oxidation , 1999 .

[4]  T. Matsuo,et al.  Cumene oxidation by cis-[RuIV(bpy)2(py)(O)]2+, revisited. , 2004, Inorganic chemistry.

[5]  H. Gray,et al.  Preface on making oxygen. , 2008, Inorganic chemistry.

[6]  B. Forbush,et al.  COOPERATION OF CHARGES IN PHOTOSYNTHETIC O2 EVOLUTION–I. A LINEAR FOUR STEP MECHANISM , 1970, Photochemistry and photobiology.

[7]  V. Batista,et al.  QM/MM Models of the O2-Evolving Complex of Photosystem II. , 2006, Journal of chemical theory and computation.

[8]  T. Meyer,et al.  Mechanism of Water Oxidation by the μ-Oxo Dimer [(bpy)2(H2O)RuIIIORuIII(OH2)(bpy)2]4+ , 2000 .

[9]  R. Thummel,et al.  A new family of Ru complexes for water oxidation. , 2005, Journal of the American Chemical Society.

[10]  T. Meyer,et al.  Oxidation of hydroquinones by [(bpy)2(py)RuIV(O)]2+ and [(bpy)2(py)RuIII(OH)]2+. Proton-coupled electron transfer , 1992 .

[11]  Kwok‐yin Wong,et al.  Electrochemistry of oxo-bridged ruthenium dimers with 4,4′-dichloro- and 5,5′-dichloro-2,2′-bipyridine and their catalytic properties towards water oxidation , 1995 .

[12]  I. Romero,et al.  RuO complexes as catalysts for oxidative transformations, including the oxidation of water to molecular dioxygen , 2006 .

[13]  J. K. Hurst,et al.  A molecular water-oxidation catalyst derived from ruthenium diaqua bis(2,2'-bipyridyl-5,5'-dicarboxylic acid) , 1987 .

[14]  V. Pecoraro,et al.  Reflections on Small Molecule Manganese Models that Seek to Mimic Photosynthetic Water Oxidation Chemistry. , 2008, Coordination chemistry reviews.

[15]  J. Sauvage,et al.  Synthesis and study of mononuclear ruthenium(II) complexes of sterically hindering diimine chelates. Implications for the catalytic oxidation of water to molecular oxygen , 1986 .

[16]  James Barber,et al.  Architecture of the Photosynthetic Oxygen-Evolving Center , 2004, Science.

[17]  M. Grätzel Photoelectrochemical cells : Materials for clean energy , 2001 .

[18]  N. C. Pramanik,et al.  Chemical oxidation of water to dioxygen. Homogeneous catalysis by a ruthenium aquo-complex , 1997 .

[19]  T. Meyer,et al.  Synthesis and spectral and redox properties of three triply bridged complexes of ruthenium , 1989 .

[20]  Functionalized polypyrroles. New molecular materials for electrocatalysis and related applications , 1989 .

[21]  Daniel G. Nocera,et al.  In Situ Formation of an Oxygen-Evolving Catalyst in Neutral Water Containing Phosphate and Co2+ , 2008, Science.

[22]  C. Cramer,et al.  Computational Electrochemistry: The Aqueous Ru3+|Ru2+ Reduction Potential , 2007 .

[23]  H. Taube,et al.  Organic molecules as bridging groups in electron-transfer reactions , 1969 .

[24]  K. Sanderson Chemistry: The photon trap , 2008, Nature.

[25]  I. Romero,et al.  Synthesis, structure, and acid-base and redox properties of a family of new Ru(II) isomeric complexes containing the trpy and the dinucleating Hbpp ligands. , 2003, Inorganic chemistry.

[26]  Susan W. Gersten,et al.  Catalytic oxidation of water by an oxo-bridged ruthenium dimer , 1982 .

[27]  Paul Kögerler,et al.  An all-inorganic, stable, and highly active tetraruthenium homogeneous catalyst for water oxidation. , 2008, Angewandte Chemie.

[28]  C. Che,et al.  Alkene cis-dihydroxylation by [(Me3tacn)(CF3CO2)RuVI O2)]ClO4(Me(3)tacn = 1,4,7-Trimethyl-1,4,7-triazacyclononane): structural characterization of [3 + 2] cycloadducts and kinetic studies. , 2005, Journal of the American Chemical Society.

[29]  H Holden Thorp,et al.  The possible role of proton-coupled electron transfer (PCET) in water oxidation by photosystem II. , 2007, Angewandte Chemie.

[30]  J. K. Hurst,et al.  Resonance Raman, Optical Spectroscopic, and EPR Characterization of the Higher Oxidation States of the Water Oxidation Catalyst, cis,cis-[(bpy)2Ru(OH2)]2O4+ , 2000 .

[31]  T. Meyer,et al.  Proton-coupled electron transfer. , 2007, Chemical reviews.

[32]  A. Llobet Synthesis, spectral and redox properties of a new series of aqua complexes of ruthenium(II) , 1994 .

[33]  J. K. Hurst,et al.  Dynamical investigations of the catalytic mechanisms of water oxidation by the [(bpy)2Ru(OH2)]2O4+ ion , 1994 .

[34]  T. Meyer,et al.  Redox properties and ligand loss chemistry in aqua/hydroxo/oxo complexes derived from cis- and trans-[(bpy)2RuII(OH2)2]2+ , 1988 .

[35]  J. A. Crayston,et al.  Structure of Tetrameric Aqua Ruthenium(IV): an Investigation by Ruthenium K Edge EXAFS , 1998 .

[36]  C. Shannon,et al.  A diruthenium-substituted polyoxometalate as an electrocatalyst for oxygen generation. , 2004, Journal of the American Chemical Society.

[37]  C. M. Elliott,et al.  Characterization and Catalytic Activity of Covalently Linked Bipyridyl Ruthenium OXO Dimers , 1992 .

[38]  Susan W. Gersten,et al.  Structure and redox properties of the water-oxidation catalyst [(bpy)2(OH2)RuORu(OH2)(bpy)2]4+ , 1985 .

[39]  Antoni Llobet,et al.  A new Ru complex capable of catalytically oxidizing water to molecular dioxygen. , 2004, Journal of the American Chemical Society.

[40]  A. Deronzier,et al.  Synthesis, structure, and redox and catalytic properties of a new family of ruthenium complexes containing the tridentate bpea ligand. , 2001, Inorganic chemistry.

[41]  J. K. Hurst,et al.  Pathways for water oxidation catalyzed by the (.mu.-oxo)bis[aquabis(bipyridine)ruthenium](4+) ion , 1992 .

[42]  J. K. Hurst,et al.  Mechanisms of water oxidation catalyzed by the cis,cis-[(bpy)2Ru(OH2)]2O4+ ion. , 2004, Journal of the American Chemical Society.

[43]  R. Thummel,et al.  Preparation and study of a family of dinuclear Ru(II) complexes that catalyze the decomposition of water. , 2008, Inorganic chemistry.

[44]  Gianfranco Scorrano,et al.  Polyoxometalate embedding of a tetraruthenium(IV)-oxo-core by template-directed metalation of [gamma-SiW10O36]8-: a totally inorganic oxygen-evolving catalyst. , 2008, Journal of the American Chemical Society.

[45]  A. Rutherford,et al.  Artificial systems related to light driven electron transfer processes in PSII , 2008 .

[46]  T. Meyer,et al.  The remarkable reactivity of high oxidation state ruthenium and osmium polypyridyl complexes. , 2003, Inorganic chemistry.

[47]  W. Saenger,et al.  Where Water Is Oxidized to Dioxygen: Structure of the Photosynthetic Mn4Ca Cluster , 2006, Science.

[48]  T. Meyer,et al.  Water Oxidation by [(tpy)(H2O)2RuIIIORuIII(H2O)2(tpy)]4+ , 1998 .

[49]  M. Baik,et al.  Electronic structure of the water-oxidation catalyst [(bpy)2(OHx)RuORu(OHy)(bpy)2]z+: weak coupling between the metal centers is preferred over strong coupling. , 2004, Journal of the American Chemical Society.

[50]  Vincenzo Balzani,et al.  Luminescent and Redox-Active Polynuclear Transition Metal Complexes. , 1996, Chemical reviews.

[51]  T. Meyer,et al.  Mechanism of Water Oxidation Catalyzed by the μ-Oxo Dimer [(bpy)2(OH2)RuIIIORuIII(OH2)(bpy)2]4+ , 1997 .

[52]  Holger Dau,et al.  Eight steps preceding O-O bond formation in oxygenic photosynthesis--a basic reaction cycle of the Photosystem II manganese complex. , 2007, Biochimica et biophysica acta.

[53]  M. Grätzel,et al.  Spontaneous oxidation of water to oxygen by the mixed-valence µ-oxo ruthenium dimer L2(H2O)RuIII–O–RuIV(OH)L2(L = 2,2′-bipyridyl-5,5′-dicarboxylic acid) , 1988 .

[54]  I. Romero,et al.  Can the disproportion of oxidation state III be favored in RuII-OH2/RuIV=O systems? , 2006, Journal of the American Chemical Society.

[55]  Richard A. Hammitt,et al.  Synthetic approaches to polypyridyl bridging ligands with proximal multidentate binding sites. , 2006, The Journal of organic chemistry.

[56]  B. P. Sullivan,et al.  Synthesis, structure, and spectroscopic, photochemical, redox, and catalytic properties of ruthenium(II) isomeric complexes containing dimethyl sulfoxide, chloro, and the dinucleating bis(2-pyridyl)pyrazole ligands. , 2003, Inorganic chemistry.

[57]  L. Heerman,et al.  Electrochemical oxidation of ruthenium(IV) at platinum rotating disk electrodes: preparation and characterization of a tetrameric ruthenium(4.25) species , 1988 .

[58]  F. Teixidor,et al.  Extraordinary Overoxidation Resistance Increase in Self‐Doped Polypyrroles by Using Non‐conventional Low Charge‐Density Anions , 2002 .

[59]  Michael C. Zerner,et al.  Semiempirical Molecular Orbital Methods , 2007 .

[60]  Thomas J. Meyer,et al.  Zur möglichen Rolle des protonengekoppelten Elektronentransfers (PCET) bei der Oxidation von Wasser durch das Photosystem II , 2007 .

[61]  James M Mayer,et al.  Proton-coupled electron transfer: a reaction chemist's view. , 2004, Annual review of physical chemistry.

[62]  A. Boussac,et al.  Water Photolysis in Biology , 2004, Science.

[63]  S. Bernhard,et al.  Cyclometalated iridium(III) Aquo complexes: efficient and tunable catalysts for the homogeneous oxidation of water. , 2008, Journal of the American Chemical Society.

[64]  K. Tsuge,et al.  Electrochemical Oxidation of Water to Dioxygen Catalyzed by the Oxidized Form of the Bis(ruthenium – hydroxo) Complex in H2O , 2000 .

[65]  G. Brudvig,et al.  Water-splitting chemistry of photosystem II. , 2006, Chemical reviews.

[66]  Antoni Llobet,et al.  Ru complexes that can catalytically oxidize water to molecular dioxygen. , 2008, Inorganic chemistry.

[67]  J. K. Hurst,et al.  Structural Investigations of the Catalytic Mechanisms of Water Oxidation by the [(bpy)2Ru(OH2)]2O4+ Ion , 1994 .

[68]  T. Meyer,et al.  Water oxidation by [(bpy)2(O)RuVORuV(O)(bpy)2] 4+. An oxygen-labeling study , 1990 .

[69]  M Yagi,et al.  Molecular catalysts for water oxidation. , 2001, Chemical reviews.

[70]  J. K. Hurst,et al.  Water exchange rates in the diruthenium mu-oxo ion cis,cis-[(bpy)(2)Ru(OH(2))](2)O(4+). , 2001, Journal of the American Chemical Society.

[71]  F. Liu,et al.  Electrochemical oxidation of water by an adsorbed mu-oxo-bridged Ru complex. , 2007, Journal of the American Chemical Society.

[72]  Mu-Hyun Baik,et al.  cis,cis-[(bpy)2RuVO]2O4+ catalyzes water oxidation formally via in situ generation of radicaloid RuIV-O*. , 2006, Journal of the American Chemical Society.

[73]  Jan Kern,et al.  Towards complete cofactor arrangement in the 3.0 Å resolution structure of photosystem II , 2005, Nature.

[74]  I. Romero,et al.  Ru-hbpp-based water-oxidation catalysts anchored on conducting solid supports. , 2008, Angewandte Chemie.

[75]  A. Poater,et al.  Synthesis, Structure, and Redox Properties of a New Aqua Ruthenium Complex Containing the Tridentate [9]aneS3 and the Didentate 1,10‐Phenanthroline Ligands , 2004 .

[76]  T. Meyer,et al.  Redox properties of the oxo-bridged osmium dimer [(bpy)2(OH2)OsIIIOOsIV(OH)(bpy)2]4+. Implications for the oxidation of water to oxygen , 1986 .