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Iron and manganese oxo complexes, oxo wall and beyond

Nature Reviews Chemistry volume 4, pages 404–419 (2020)Cite this article

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Abstract

High-valent metal–oxo species with multiply-bonded M–O groups have been proposed as key intermediates in many biological and abiological catalytic oxidation reactions. These intermediates are implicated as active oxidants in alkane hydroxylation, olefin epoxidation and other oxidation reactions. For example, [FeivO(porphyrinato•−)]+ cofactors bearing π-radical porphyrinato•− ligands oxidize organic substrates in cytochrome P450 enzymes, which are common to many life forms. Likewise, high-valent Mn–oxo species are active for H2O oxidation in photosystem II. The chemistry of these native reactive species has inspired chemists to prepare highly oxidized transition-metal complexes as functional mimics. Although many synthetic Fe–O and Mn–O complexes now exist, the analogous oxo complexes of the late transition metals (groups 9–11) are rare. Indeed, late-transition-metal–oxo complexes of tetragonal (fourfold) symmetry should be electronically unstable, a rule commonly referred to as the ‘oxo wall’. A few late metal–oxos have been prepared by targeting other symmetries or unusual spin states. These complexes have been studied using spectroscopic and theoretical methods. This Review describes mononuclear non-haem Fe–O and Mn–O species, the nature of the oxo wall and recent advances in the preparation of oxo complexes of Co, Ni and Cu beyond the oxo wall.

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Fig. 1: Nature has inspired the synthesis of high-valent metal–oxo complexes.
Fig. 2: Coordination geometry, d-electron counts and spin state govern M–O bond order.
Fig. 3: Molecular and electronic structures and reactivities of Fe–O complexes.
Fig. 4: Molecular and electronic structures and reactivities of Mn–O complexes.
Fig. 5: Structures of Co–O complexes.
Fig. 6: Structures of Ni and Cu complexes.

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Acknowledgements

The authors gratefully acknowledge the contributions of their collaborators and co-workers in the cited references. W.N. acknowledges the financial support from the NRF of Korea through CRI (NRF-2012R1A3A2048842). N.L. acknowledges support from the National Science Foundation (NSF, CHE-1900380). K.R. is funded by the Deutsche Forschungsgemeinschaft (DFG, German Research Foundation) under Germany’s Excellence Strategy — EXC 2008 — 390540038 — UniSysCat and the Heisenberg professorship.

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Authors and Affiliations

  1. Department of Chemistry, University of Michigan, Ann Arbor, MI, USA

    Virginia A. Larson & Nicolai Lehnert

  2. Department of Biophysics, University of Michigan, Ann Arbor, MI, USA

    Virginia A. Larson & Nicolai Lehnert

  3. Department of Chemistry, Humboldt-Universität zu Berlin, Berlin, Germany

    Beatrice Battistella & Kallol Ray

  4. Department of Chemistry and Nano Science, Ewha Womans University, Seoul, Korea

    Wonwoo Nam

  5. School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi’an, China

    Wonwoo Nam

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Larson, V.A., Battistella, B., Ray, K. et al. Iron and manganese oxo complexes, oxo wall and beyond. Nat Rev Chem 4, 404–419 (2020). https://doi.org/10.1038/s41570-020-0197-9

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