Skip to main content

Thank you for visiting You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

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


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.

Your institute does not have access to this article

Relevant articles

Open Access articles citing this article.

Access options

Buy article

Get time limited or full article access on ReadCube.


All prices are NET prices.

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.

Accession codes

Primary accessions


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.


  1. Nugent, W. A. & Mayer, J. M. Metal-Ligand Multiple Bonds (Wiley, 1988)

    Google Scholar 

  2. Holm, R. H. Metal-centered oxygen atom transfer reactions. Chem. Rev. 87, 1401–1449 (1987)

    CAS  Article  Google Scholar 

  3. Sheldon, R. A. & Kochi, J. K. Metal-Catalyzed Oxidations of Organic Compounds (Academic, 1981)

    Google Scholar 

  4. Meunier, B. (ed.) Biomimetic Oxidations Catalyzed by Transition Metal Complexes (Imperial College Press, 2000)

    Book  Google Scholar 

  5. Yoshizawa, K. Nonradical mechanism for methane hydroxylation by iron-oxo complexes. Acc. Chem. Res. 39, 375–382 (2006)

    CAS  Article  Google Scholar 

  6. Rohde, J.-U. et al. Crystallographic and spectroscopic characterization of a nonheme Fe(IV)-O complex. Science 299, 1037–1039 (2003)

    ADS  CAS  Article  Google Scholar 

  7. Green, M. T., Dawson, J. H. & Gray, H. B. Oxoiron(IV) in chloroperoxidase compound II is basic: Implications for P450 chemistry. Science 304, 1653–1656 (2004)

    ADS  CAS  Article  Google Scholar 

  8. Somorjai, G. A. Introduction to Surface Chemistry and Catalysis (Wiley, 1994)

    Google Scholar 

  9. Ruettinger, W. & Dismukes, G. C. Synthetic water-oxidation catalysts for artificial photosynthetic water oxidation. Chem. Rev. 97, 1–24 (1997)

    CAS  Article  Google Scholar 

  10. Yagi, M. & Kaneko, M. Molecular catalysts for water oxidation. Chem. Rev. 101, 21–35 (2001)

    CAS  Article  Google Scholar 

  11. Alstrum-Acevedo, J. H., Brennaman, M. K. & Meyer, T. J. Chemical approaches to artificial photosynthesis. 2. Inorg. Chem. 44, 6802–6827 (2005)

    CAS  Article  Google Scholar 

  12. Dempsey, J. L. et al. Molecular chemistry of consequence to renewable energy. Inorg. Chem. 44, 6879–6892 (2005)

    CAS  Article  Google Scholar 

  13. Lewis, N. S. & Nocera, D. G. Powering the planet: Chemical challenges in solar energy utilization. Proc. Natl Acad. Sci. USA 103, 15729–15735 (2006)

    ADS  CAS  Article  Google Scholar 

  14. Spaltenstein, E., Conry, R. R., Critchlow, S. C. & Mayer, J. M. Low-valent rhenium-oxo complexes. 9. Synthesis, characterization, and reactivity of a formally rhenium(I) terminal oxo complex, NaRe(O)(RC≡CR)2 . J. Am. Chem. Soc. 111, 8741–8742 (1989)

    CAS  Article  Google Scholar 

  15. Anderson, T. M. et al. Late-transition metal oxo complex: K7Na9[O:PtIV(H2O)L2], L = [PW9O34]9- . Science 306, 2074–2077 (2004)

    ADS  CAS  Article  Google Scholar 

  16. Anderson, T. M. et al. Palladium-oxo complex. Stabilization of this proposed catalytic intermediate by an encapsulating polytungstate ligand. J. Am. Chem. Soc. 127, 11948–11949 (2005)

    CAS  Article  Google Scholar 

  17. Cao, R., Musaev, D. J., Morokuma, K., Takahashi, M. & Hill, C. L. Terminal gold-oxo complexes. J. Am. Chem. Soc. 129, 11118–11133 (2007)

    CAS  Article  Google Scholar 

  18. MacBeth, C. E. et al. O2 activation by nonheme iron complexes: A monomeric Fe(III)-oxo complex derived from O2 . Science 289, 938–941 (2000)

    ADS  CAS  Article  Google Scholar 

  19. Van der Boom, M. E. & Milstein, D. Cyclometalated phosphine-based pincer complexes: Mechanistic insight in catalysis, coordination, and bond activation. Chem. Rev. 103, 1759–1792 (2003)

    CAS  Article  Google Scholar 

  20. Poverenov, E. et al. Pincer “hemilabile” effect. PCN platinum(II) complexes with different amine “arm length”. Organometallics 24, 1082–1090 (2005)

    CAS  Article  Google Scholar 

  21. Murray, R. W. & Singh, M. Chemistry of dioxiranes. Reaction of dimethyldioxirane with alkynes. J. Org. Chem. 58, 5076–5080 (1993)

    CAS  Article  Google Scholar 

  22. Sassenberg, U. & Scullman, R. The emission spectrum of PtO between 3800 A and 8900 A. Phys. Scripta 28, 139–159 (1983)

    ADS  CAS  Article  Google Scholar 

  23. Schott, D., Pregosin, P. S., Albinati, A. & Rizatto, S. PGSE diffusion NMR studies on mononuclear and dinuclear cationic salts of (S)-MeO-Biphep and (R)-p-tolyl-BINAP. Inorg. Chim. Acta 360, 3203–3212 (2007)

    CAS  Article  Google Scholar 

  24. Collman, J. P., Slaughter, L. M., Eberspacher, T. A., Strassner, T. & Brauman, J. I. Mechanism of dihydrogen cleavage by high-valent metal oxo compounds: Experimental and computational studies. Inorg. Chem. 40, 6272–6280 (2001)

    CAS  Article  Google Scholar 

  25. Yang, X. & Baik, M.-H. cis,cis-[(bpy)2RuVO]2O4+ catalyzes water oxidation formally via in situ generation of radicaloid RuIV-O*. J. Am. Chem. Soc. 128, 7476–7485 (2006)

    CAS  Article  Google Scholar 

  26. Hurst, J. K. Water oxidation catalyzed by dimeric μ-oxo bridged ruthenium diimine complexes. Coord. Chem. Rev. 249, 313–328 (2005)

    CAS  Article  Google Scholar 

  27. Elizarova, G. L., Zhidomirov, G. M. & Parmon, V. N. Hydroxides of transition metals as artificial catalysts for oxidation of water to dioxygen. Catal. Today 58, 71–88 (2000)

    CAS  Article  Google Scholar 

  28. Binstead, R. A., Chronister, C. W., Ni, J., Hartshorn, C. M. & Meyer, T. J. Mechanism of water oxidation by the μ-oxo dimer [(bpy)2(H2O)RuIIIORuIII(OH2)(bpy)2]4+ . J. Am. Chem. Soc. 122, 8464–8473 (2000)

    CAS  Article  Google Scholar 

  29. Labinger, J. A. & Bercaw, J. E. Understanding and exploiting C–H bond activation. Nature 417, 507–513 (2002)

    ADS  CAS  Article  Google Scholar 

  30. Rostovtsev, V. V., Labinger, J. A., Bercaw, J. E., Lasseter, T. L. & Goldberg, K. I. Oxidation of dimethylplatinum(II) complexes with dioxygen. Organometallics 17, 4530–4531 (1998)

    CAS  Article  Google Scholar 

Download references


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.

Author information

Authors and Affiliations


Corresponding author

Correspondence to David Milstein.

Supplementary information

Supplementary Information

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

PowerPoint slides

Rights and permissions

Reprints and Permissions

About this article

Cite this article

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

Download citation

  • Received:

  • Accepted:

  • Issue Date:

  • DOI:

Further reading


By submitting a comment you agree to abide by our Terms and Community Guidelines. If you find something abusive or that does not comply with our terms or guidelines please flag it as inappropriate.


Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing