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Organometallic Models for Metal Surface Reactions: Chain Growth Involving Electrophilic Methylidynes in the Fischer–Tropsch Reaction

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Abstract

A new mechanism involving metal-bound surface electrophilic methylidynes is proposed for chain growth in the Fischer–Tropsch reaction to give 1-alkenes.

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Acknowledgements

We thank Franco Fanizzi, Tony Haynes, Graham Hutchings, Peijun Hu, and Luciana Maresca for interesting discussions.

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Authors and Affiliations

  1. Department of Chemistry, The University of Sheffield, Sheffield, S3 7HF, UK

    Peter M. Maitlis

  2. Dipartimento di Chimica Fisica ed Inorganica, Università di Bologna, Viale Risorgimento 4, Bologna, 40316, Italy

    Valerio Zanotti

Authors
  1. Peter M. Maitlis
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  2. Valerio Zanotti
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Corresponding author

Correspondence to Peter M. Maitlis.

Appendix

Appendix

A referee has asked us to propose some experiments to support these ideas. Since the initial CO cleavage and the subsequent C–H formation steps in the Fischer–Tropsch process are probably fast on the catalytically active metal surfaces, the C–C coupling is likely to be the slowest (i.e. rate-determining) step of the overall process. One approach would thus be to increase the rate by increasing the electrophilicity of the methylidyne. This could be achievable either electrochemically or by adding a very strong Lewis acid. Komaya, Boffa, Bell and their coworkers have shown that the rate of methane formation in CO hydrogenation over Rh decorated by various metal oxides is dependent on the Lewis acidity of the oxide [34–36]. Given the very sensitive analytical techniques now available it should be relatively straightforward to extend this experiment to ascertain how the degree of chain lengthening (i.e. the rate of formation of products C>1) is affected by different Lewis acids on a number of metals with Fischer–Tropsch activity, and comparing them to the rates of methane production.

It is also interesting that addition of potassium to a Rh(111) surface stabilised CH2(ad) caused it to dimerise to ethylene [37].

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Maitlis, P.M., Zanotti, V. Organometallic Models for Metal Surface Reactions: Chain Growth Involving Electrophilic Methylidynes in the Fischer–Tropsch Reaction. Catal Lett 122, 80–83 (2008). https://doi.org/10.1007/s10562-007-9359-3

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