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Ligand Effects on the Reactivity of [CoX]+ (X = CN, F, Cl, Br, O, OH) Towards CO2: Gas-Phase Generation of the Elusive Cyanoformate by [Co(CN)]+ and [Fe(CN)]+

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Abstract

The thermal reactions of [CoX]+ (X = CN, F, Cl, Br, O, OH) with carbon dioxide have been investigated experimentally and theoretically by using electrospray ionization mass spectrometry (ESI-MS) and density functional theory. Surprisingly, in contrast to the complete inertness of [CoX]+ (X = F, Cl, Br, O, OH) toward carbon dioxide, [Co(CN)]+ activates carbon dioxide to form the elusive [NCCO2Co]+ ion in the gas phase. Mechanistic investigation into this ligand-controlled CO2 activation via C_C bond formation, mediated by a first-row late transition-metal complex, reveals that the inertness of [CoX]+ (X = F, Cl, Br, O, OH) is due to kinetic barriers located above the entrance asymptote. The exception is the [Co(CN)]+/CO2 couple, for which the thermal C–C bond formation is both thermochemically and kinetically accessible. Interestingly, a cyanoformate ligand is most likely also formed in the reaction of [Fe(CN)]+ with CO2; cyanoformate formation had been suggested earlier as a protective mechanism to prevent cyanide complexation to the iron-containing active site of the enzyme ACC oxidase (Murphy et al., in Science 344:75–78, 2014).

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Acknowledgements

This work has been supported by the Fonds der Chemischen Industrie, the Deutsche Forschungsgemeinschaft (DFG), and the Cluster of Excellence “Unifying Concepts in Catalysis” (coordinated by the Technische Universität Berlin and funded by the DFG). NJR gratefully acknowledges support from the QUT Institute for Future Environments (IFE) and the Australian Research Council (ARC) for an ARC Discovery Early Career Researcher Award (DECRA) (project number DE170100677). For computational resources, the Institut für Mathematik at the Technische Universität Berlin is acknowledged. Dr. Shaodong Zhou is appreciated for suggestions and comments. We thank Andrea Beck and Dr. Thomas Weiske for technical assistance.

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  1. Institut für Chemie, Technische Universität Berlin, Straβe des 17. Juni 135, 10623, Berlin, Germany

    Marjan Firouzbakht, Maria Schlangen, Martin Kaupp & Helmut Schwarz

  2. Institute of Nanotechnology (INT), Karlsruhe Institute of Technology (KIT), Hermann-von-Helmholtz-Platz 1, 76344, Eggenstein-Leopoldshafen, Germany

    Nicole J. Rijs

  3. School of Chemistry, Physics and Mechanical Engineering, Queensland University of Technology (QUT), 2 George Street, Brisbane, QLD, 4001, Australia

    Nicole J. Rijs

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  1. Marjan Firouzbakht
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Correspondence to Martin Kaupp or Helmut Schwarz.

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In memoriam Professor George A. Olah.

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Firouzbakht, M., Rijs, N.J., Schlangen, M. et al. Ligand Effects on the Reactivity of [CoX]+ (X = CN, F, Cl, Br, O, OH) Towards CO2: Gas-Phase Generation of the Elusive Cyanoformate by [Co(CN)]+ and [Fe(CN)]+. Top Catal 61, 575–584 (2018). https://doi.org/10.1007/s11244-018-0903-8

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