Hydrogen-transfer catalysis with Cp*IrIII complexes: The influence of the ancillary ligands

U Hintermair, Jesus Campos, Timothy P. Brewster, Lucas M Pratt, Nathan D Schley, Robert H Crabtree

Research output: Contribution to journalArticle

64 Citations (Scopus)
58 Downloads (Pure)

Abstract

Fourteen Cp*IrIII complexes, bearing various combinations of N- and C-spectator ligands, are assayed in hydrogen-transfer catalysis from isopropyl alcohol to acetophenone under various conditions to investigate ligand effects in this widely used reaction. The new cationic complexes bearing monodentate pyridine and N-heterocyclic carbene (NHC) ligands were characterized crystallographically and by variable-temperature nuclear magnetic resonance (VT-NMR). Control experiments and mercury poisoning tests showed that iridium(0) nanoparticles, although active in the reaction, are not responsible for the high activity observed for the most active precatalyst [Cp*Ir(IMe)2Cl]BF4 (6). For efficient catalysis, it was found necessary to have both NHCs in monodentate form; tying them together in a bis-NHC chelate ligand gave greatly reduced activity. The kinetics of the base-assisted reaction showed induction periods as well as deactivation processes, and H/D scrambling experiments cast some doubt on the classical monohydride mechanism.
Original languageEnglish
Pages (from-to)99-108
Number of pages10
JournalACS Catalysis
Volume4
Issue number1
Early online date9 Dec 2013
DOIs
Publication statusPublished - 3 Jan 2014

Fingerprint Dive into the research topics of 'Hydrogen-transfer catalysis with Cp*Ir<sup>III</sup> complexes: The influence of the ancillary ligands'. Together they form a unique fingerprint.

Cite this