Topics in Catalysis

, Volume 61, Issue 7–8, pp 575–584 | Cite as

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)]+

  • Marjan Firouzbakht
  • Nicole J. Rijs
  • Maria Schlangen
  • Martin Kaupp
  • Helmut Schwarz
Original Paper


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).


Carbon dioxide Cobalt complexes C–C bond formation Ligand effect ESI-MS Cyano ligand 



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.

Compliance with Ethical Standards

Conflict of interest

This manuscript has not been submitted elsewhere for consideration, and the authors declare not competing financial interests.

Supplementary material

11244_2018_903_MOESM1_ESM.docx (279 kb)
Supplementary material 1 (DOCX 279 KB)


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Authors and Affiliations

  1. 1.Institut für ChemieTechnische Universität BerlinBerlinGermany
  2. 2.Institute of Nanotechnology (INT)Karlsruhe Institute of Technology (KIT)Eggenstein-LeopoldshafenGermany
  3. 3.School of Chemistry, Physics and Mechanical EngineeringQueensland University of Technology (QUT)BrisbaneAustralia

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