TY - JOUR
T1 - Consecutive thermal H2 and light-induced O2 evolution from water promoted by a metal complex
AU - Kohl, Stephan W.
AU - Weiner, Lev
AU - Schwartsburd, Leonid
AU - Konstantinovski, Leonid
AU - Shimon, Linda J.W.
AU - David, Yehoshoa Ben
AU - Iron, Mark A.
AU - Milstein, David
PY - 2009/4/3
Y1 - 2009/4/3
N2 - Discovery of an efficient artificial catalyst for the sunlight-driven splitting of water into dioxygen and dihydrogen is a major goal of renewable energy research. We describe a solution-phase reaction scheme that leads to the stoichiometric liberation of dihydrogen and dioxygen in consecutive thermal- and light-driven steps mediated by mononuclear, well-defined ruthenium complexes. The initial reaction of water at 25°C with a dearomatized ruthenium (II) [Ru(II)] pincer complex yields a monomeric aromatic Ru(II) hydrido-hydroxo complex that, on further reaction with water at 100°C, releases H2 and forms a cis dihydroxo complex. Irradiation of this complex in the 320-to-420-nanometer range liberates oxygen and regenerates the starting hydrido-hydroxo Ru(II) complex, probably by elimination of hydrogen peroxide, which rapidly disproportionates. Isotopic labeling experiments with H 2 17O and H2 18O show unequivocally that the process of oxygen-oxygen bond formation is intramolecular, establishing a previously elusive fundamental step toward dioxygen-generating homogeneous catalysis.
AB - Discovery of an efficient artificial catalyst for the sunlight-driven splitting of water into dioxygen and dihydrogen is a major goal of renewable energy research. We describe a solution-phase reaction scheme that leads to the stoichiometric liberation of dihydrogen and dioxygen in consecutive thermal- and light-driven steps mediated by mononuclear, well-defined ruthenium complexes. The initial reaction of water at 25°C with a dearomatized ruthenium (II) [Ru(II)] pincer complex yields a monomeric aromatic Ru(II) hydrido-hydroxo complex that, on further reaction with water at 100°C, releases H2 and forms a cis dihydroxo complex. Irradiation of this complex in the 320-to-420-nanometer range liberates oxygen and regenerates the starting hydrido-hydroxo Ru(II) complex, probably by elimination of hydrogen peroxide, which rapidly disproportionates. Isotopic labeling experiments with H 2 17O and H2 18O show unequivocally that the process of oxygen-oxygen bond formation is intramolecular, establishing a previously elusive fundamental step toward dioxygen-generating homogeneous catalysis.
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U2 - 10.1126/science.1168600
DO - 10.1126/science.1168600
M3 - Article
C2 - 19342584
AN - SCOPUS:64249155542
VL - 324
SP - 74
EP - 77
JO - Science
JF - Science
SN - 0036-8075
IS - 5923
ER -