om7b00492_si_001.pdf (2.69 MB)
Ligand Tuning in Pyridine-Alkoxide Ligated Cp*IrIII Oxidation Catalysts
journal contribution
posted on 2017-09-08, 15:36 authored by Emma V. Sackville, Gabriele Kociok-Köhn, Ulrich HintermairSix
novel derivatives of pyridine-alkoxide ligated Cp*IrIII complexes, potent precursors for homogeneous water and C–H
oxidation catalysts, have been synthesized, characterized, and analyzed
spectroscopically and kinetically for ligand effects. Variation of
alkoxide and pyridine substituents was found to affect their solution
speciation, activation behavior, and oxidation kinetics. Application
of these precursors to catalytic C–H oxidation of ethyl benzenesulfonate
with aqueous sodium periodate showed that the ligand substitution
pattern, solution pH, and solvent all have pronounced influences on
initial rates and final conversion values. Correlation with O2 evolution profiles during C–H oxidation catalysis
showed these competing reactions to occur sequentially, and demonstrates
how it is possible to tune the activity and selectivity of the active
species through the N^O ligand structure.