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

Abstract

Terminal oxo complexes of transition metals have critical roles in various biological and chemical processes1,2. For example, the catalytic oxidation of organic molecules3,4, some oxidative enzymatic transformations5,6,7, and the activation of dioxygen on metal surfaces8 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 splitting9,10,11,12,13. 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 destabilized2. 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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Figure 1: Preparation and DFT structure of complex 2.
Figure 2: XANES spectra of complexes and Fourier transform magnitudes of EXAFS data.
Figure 3: Reactivity of complex 2.
Figure 4: ORTEP views of molecules of 3 and 4 with the thermal ellipsoids at 50% probability.

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Primary accessions

DDBJ/GenBank/EMBL

Data deposits

Crystallographic data for complexes 3 and 4 have been deposited in the Cambridge Crystallographic Data Centre, under accession numbers 695884 and 695883, respectively.

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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.

Author Contributions E.P.: synthesis, characterization, reactivity studies of complexes and manuscript writing. I.E. and J.M.L.M.: DFT calculations and manuscript writing. A.I.F.: X-ray absorption spectroscopy studies. Y.B.-D.: synthesis of the PCN ligand and dioxirane. L.J.W.S. and G.L.: single-crystal X-ray diffraction analysis. L.K.: NMR studies. D.M.: design and direction of the project and manuscript writing.

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Correspondence to David Milstein.

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This file contains Supplementary Notes incorporating Supplementary Tables 1S-3S, Supplementary Figures 1S-8S with Legends and Supplementary References (PDF 578 kb)

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Poverenov, E., Efremenko, I., Frenkel, A. et al. Evidence for a terminal Pt(iv)-oxo complex exhibiting diverse reactivity. Nature 455, 1093–1096 (2008). https://doi.org/10.1038/nature07356

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