Abstract
| Original language | English |
|---|---|
| Pages (from-to) | 3578-3588 |
| Number of pages | 11 |
| Journal | Organometallics |
| Volume | 36 |
| Issue number | 18 |
| Early online date | 8 Sep 2017 |
| DOIs | |
| Publication status | Published - 25 Sep 2017 |
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Ligand Tuning in Pyridine-Alkoxide Ligated Cp*Ir III Oxidation Catalysts. / Sackville, Emma V.; Kociok-Köhn, Gabriele; Hintermair, Ulrich.
In: Organometallics, Vol. 36, No. 18, 25.09.2017, p. 3578-3588.Research output: Contribution to journal › Article
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TY - JOUR
T1 - Ligand Tuning in Pyridine-Alkoxide Ligated Cp*Ir III Oxidation Catalysts
AU - Sackville, Emma V.
AU - Kociok-Köhn, Gabriele
AU - Hintermair, Ulrich
PY - 2017/9/25
Y1 - 2017/9/25
N2 - Six 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.
AB - Six 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.
U2 - 10.1021/acs.organomet.7b00492
DO - 10.1021/acs.organomet.7b00492
M3 - Article
VL - 36
SP - 3578
EP - 3588
JO - Organometallics
JF - Organometallics
SN - 0276-7333
IS - 18
ER -