The use of halogen bonding as a tool to construct the catalyst backbone is reported. Specifically, pyridyl- and iodotetrafluoroaryl-substituted phosphines were assembled in the presence of a rhodium(I) precursor to form the corresponding halogen-bonded complex XBphos-Rh. The presence of fluorine substituents at the iodo-containing supramolecular motif was not necessary for halogen bonding to occur due to the template effect exerted by the rhodium center during formation of the halogen-bonded complex. The halogen-bonded supramolecular complexes were successfully tested in the catalytic hydroboration of terminal alkynes.
![](https://www.iciq.org/wp-content/uploads/2018/02/Screen-Shot-2018-02-21-at-11.48.56.png)