Evidence for a terminal Pt(iv)-oxo complex exhibiting diverse reactivity

Elena Poverenov, Irena Efremenko, Anatoly I. Frenkel, Yehoshoa Ben-David, Linda J W Shimon, Gregory Leitus, Leonid Konstantinovski, Jan M L Martin, David Milstein

Research output: Contribution to journalArticle

124 Citations (Scopus)

Abstract

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.

Original languageEnglish
Pages (from-to)1093-1096
Number of pages4
JournalNature
Volume455
Issue number7216
DOIs
Publication statusPublished - Oct 23 2008

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Water
Ligands
Transition metals
Electrons
Chemical activation
Oxygen
Oxidation
Photosynthesis
Molecular oxygen
Catalytic oxidation
Metals
Molecules

ASJC Scopus subject areas

  • General

Cite this

Poverenov, E., Efremenko, I., Frenkel, A. I., Ben-David, Y., Shimon, L. J. W., Leitus, G., ... Milstein, D. (2008). Evidence for a terminal Pt(iv)-oxo complex exhibiting diverse reactivity. Nature, 455(7216), 1093-1096. https://doi.org/10.1038/nature07356

Evidence for a terminal Pt(iv)-oxo complex exhibiting diverse reactivity. / Poverenov, Elena; Efremenko, Irena; Frenkel, Anatoly I.; Ben-David, Yehoshoa; Shimon, Linda J W; Leitus, Gregory; Konstantinovski, Leonid; Martin, Jan M L; Milstein, David.

In: Nature, Vol. 455, No. 7216, 23.10.2008, p. 1093-1096.

Research output: Contribution to journalArticle

Poverenov, E, Efremenko, I, Frenkel, AI, Ben-David, Y, Shimon, LJW, Leitus, G, Konstantinovski, L, Martin, JML & Milstein, D 2008, 'Evidence for a terminal Pt(iv)-oxo complex exhibiting diverse reactivity', Nature, vol. 455, no. 7216, pp. 1093-1096. https://doi.org/10.1038/nature07356
Poverenov E, Efremenko I, Frenkel AI, Ben-David Y, Shimon LJW, Leitus G et al. Evidence for a terminal Pt(iv)-oxo complex exhibiting diverse reactivity. Nature. 2008 Oct 23;455(7216):1093-1096. https://doi.org/10.1038/nature07356
Poverenov, Elena ; Efremenko, Irena ; Frenkel, Anatoly I. ; Ben-David, Yehoshoa ; Shimon, Linda J W ; Leitus, Gregory ; Konstantinovski, Leonid ; Martin, Jan M L ; Milstein, David. / Evidence for a terminal Pt(iv)-oxo complex exhibiting diverse reactivity. In: Nature. 2008 ; Vol. 455, No. 7216. pp. 1093-1096.
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