Simple NMR predictors of catalytic hydrogenation activity for [Rh(cod)Cl(NHC)] complexes featuring fluorinated NHC ligands

• Main Authors: Jamil, Mohamad Shazwan Shah, Alkaabi, Sultan, Brisdon, Alan K.
• Format: Article
• Published: Royal Society of Chemistry 2019
• Subjects: QD Chemistry
• Online Access: http://eprints.utm.my/id/eprint/87744/; http://dx.doi.org/10.1039/c9dt01219b
• Institution: Universiti Teknologi Malaysia

A series of imidazolium salts precursors for N-heterocyclic carbenes (NHCs) featuring fluoroaryl substituents have been prepared along with their selenides and rhodium complexes. Tests of the catalytic activity of the [Rh(cod)Cl(NHC)] complexes in the transfer hydrogenation of acetophenone with iPrOH shows that the rhodium complexes bearing fluorinated NHCs are better than their non-fluorinated counterparts. The order of activity being 4-F-C6H4 < 2,4-F2-C6H3 < 2,4,5-F3-C6H2 < 2,6-F2-C6H3 < 2,4,6-F3-C6H2. This order of reactivity is consistent with a number of simple NMR measures of the electronic properties of these systems, including 1JCH of the NHC·HBF4 salts, δ(77Se) of the NHC selenides and 1JRh-C and δ(13Ccarbene) of the [Rh(cod)Cl(NHC)] complexes.