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. 2018 Feb 19;9(15):3644-3648.
doi: 10.1039/c8sc00233a. eCollection 2018 Apr 21.

XBphos-Rh: a halogen-bond assembled supramolecular catalyst

Lucas Carreras  1 , Marta Serrano-Torné  1 , Piet W N M van Leeuwen  2 , Anton Vidal-Ferran  1   3
Affiliations

XBphos-Rh: a halogen-bond assembled supramolecular catalyst

Lucas Carreras et al. Chem Sci. .

Abstract

The use of halogen bonding as a tool to construct a 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.

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Figures

Scheme 1
Scheme 1. Supramolecular halogen-bonded catalysts (A: halogen bond acceptor; X: halogen bond donor; M: metal centre).
Scheme 2
Scheme 2. Synthesis of halogen-bonded rhodium(i) chelates.
Fig. 1
Fig. 1. Crystal structures of XBphos-Rh (A) and 5 (B). Hydrogen atoms and the BArF unit have been omitted for the sake of clarity. Colour scheme: C: black, P: orange, Rh: green, F: green, N: blue, I: purple, O: red. Atomic displacement ellipsoids are drawn at a 50% probability.
Fig. 2
Fig. 2. Electrostatic potential surfaces at an isovalue of 0.001 a.u.
See this image and copyright information in PMC

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