TY - JOUR
T1 - Evidence for a terminal Pt(iv)-oxo complex exhibiting diverse reactivity
AU - Poverenov, Elena
AU - Efremenko, Irena
AU - Frenkel, Anatoly I.
AU - Ben-David, Yehoshoa
AU - Shimon, Linda J.W.
AU - Leitus, Gregory
AU - Konstantinovski, Leonid
AU - Martin, Jan M.L.
AU - Milstein, David
N1 - Funding Information:
Acknowledgements This research was supported in part by the Israeli Science Foundation, by the German Federal Ministry of Education and Research (BMBF) under the framework of the German-Israeli Cooperation, by the Minerva Foundation, Munich, Germany, and by the Helen and Martin Kimmel Center for Molecular Design. A.I.F. acknowledges support from the US Department of Energy (DE-FG02-03ER15476). Beamline X18B is supported by the NSLS through the Divisions of Materials and Chemical Sciences of the US DOE, and the Synchrotron Catalysis Consortium through the US DOE (DE-FG02-05ER15688). We thank Q. Wang for help with the synchrotron measurements. D.M. holds the Israel Matz Professorial Chair.
PY - 2008/10/23
Y1 - 2008/10/23
N2 - Terminal oxo complexes of transition metals have critical roles in various biological and chemical processes. For example, the catalytic oxidation of organic molecules, some oxidative enzymatic transformations, and the activation of dioxygen on metal surfaces are all thought to involve oxo complexes. Moreover, they are believed to be key intermediates in the photocatalytic oxidation of water to give molecular oxygen, a topic of intensive global research aimed at artificial photosynthesis and water splitting. The terminal oxo ligand is a strong π-electron donor, so it readily forms stable complexes with high-valent early transition metals. As the d orbitals are filled up with valence electrons, the terminal oxo ligand becomes destabilized. Here we present evidence for a dn (n > 5) terminal oxo complex that is not stabilized by an electron withdrawing ligand framework. This d6 Pt(iv) complex exhibits reactivity as an inter- and intramolecular oxygen donor and as an electrophile. In addition, it undergoes a water activation process leading to a terminal dihydroxo complex, which may be relevant to the mechanism of catalytic reactions such as water oxidation.
AB - Terminal oxo complexes of transition metals have critical roles in various biological and chemical processes. For example, the catalytic oxidation of organic molecules, some oxidative enzymatic transformations, and the activation of dioxygen on metal surfaces are all thought to involve oxo complexes. Moreover, they are believed to be key intermediates in the photocatalytic oxidation of water to give molecular oxygen, a topic of intensive global research aimed at artificial photosynthesis and water splitting. The terminal oxo ligand is a strong π-electron donor, so it readily forms stable complexes with high-valent early transition metals. As the d orbitals are filled up with valence electrons, the terminal oxo ligand becomes destabilized. Here we present evidence for a dn (n > 5) terminal oxo complex that is not stabilized by an electron withdrawing ligand framework. This d6 Pt(iv) complex exhibits reactivity as an inter- and intramolecular oxygen donor and as an electrophile. In addition, it undergoes a water activation process leading to a terminal dihydroxo complex, which may be relevant to the mechanism of catalytic reactions such as water oxidation.
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U2 - 10.1038/nature07356
DO - 10.1038/nature07356
M3 - Article
AN - SCOPUS:54549111361
VL - 455
SP - 1093
EP - 1096
JO - Nature
JF - Nature
SN - 0028-0836
IS - 7216
ER -