Moving from Fuel to Feedstock: Selective Hydrocarbon Activation using Rhodium and Iridium Complexes

Paul A. Morton, Stephen M. Mansell

Research output: Contribution to journalReview articlepeer-review

2 Citations (Scopus)
41 Downloads (Pure)


Carbon-hydrogen bond activations and their subsequent functionalisation have long been an important target in chemistry because C‐H bonds are ubiquitous throughout nature, making C‐H derivatisation reactions highly desirable. The selective and efficient functionalisation of this bond into many more useful carbon-element bonds (for example, C‐B, C‐Si, C‐O and C‐S bonds) would have many uses in pharmaceutical and bulk chemical synthesis. Activation of the C‐H bond is, however, challenging due to the high strength and low bond-polarity of this bond rendering its cleavage unfavourable. With the correct choice of reagents and systems, especially those utilising directing groups, kinetically and thermodynamically favourable catalytic processes have been developed. However, a key remaining challenge is the development of undirected, intermolecular reactions using catalysts that are both selective and active enough to make useful processes. In this review, the progress towards optimising Group 9 C‐H activation catalysts is discussed, particularly focusing on undirected reactions that are kinetically more difficult, starting with a brief history of C‐H activation, identifying the importance of auxiliary ligands including the nature of anionic ligand (for example, cyclopentadienyl, indenyl, fluorenyl and trispyrazolylborate) and neutral ligands (such as phosphines, carbonyl, alkenes and N-heterocyclic carbenes (NHCs)) that contribute towards the stability and reactivity of these metal complexes. The tethering of the anionic ligand to strong σ-donating ligands is also briefly discussed. The focus of this review is primarily on the Group 9 metals rhodium and iridium, however, C‐H activation using Group 8 and 10 metals are compared where useful. The most recent advances in this field include the development of C‐H borylation of many small hydrocarbon substrates such as arenes, heterocycles and N-alkanes as well as the more challenging substrate methane.
Original languageEnglish
Pages (from-to)333-348
Number of pages16
JournalJohnson Matthey Technology Review
Issue number3
Early online date16 Feb 2023
Publication statusPublished - 8 Jul 2023


  • Electrochemistry
  • Metals and Alloys
  • Process Chemistry and Technology

ASJC Scopus subject areas

  • Metals and Alloys
  • Process Chemistry and Technology
  • Electrochemistry


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