Ligand Tuning in Pyridine-Alkoxide Ligated Cp*Ir III Oxidation Catalysts

Emma V. Sackville; Gabriele Kociok-Köhn; Ulrich Hintermair

doi:10.1021/acs.organomet.7b00492

Ligand Tuning in Pyridine-Alkoxide Ligated Cp*Ir III Oxidation Catalysts

Emma V. Sackville, Gabriele Kociok-Köhn, Ulrich Hintermair

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Abstract

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.

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	https://doi.org/10.1021/acs.organomet.7b00492
Publication status	Published - 25 Sep 2017

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title = "Ligand Tuning in Pyridine-Alkoxide Ligated Cp*Ir III Oxidation Catalysts",

abstract = "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.",

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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 -

Ligand Tuning in Pyridine-Alkoxide Ligated Cp*Ir III Oxidation Catalysts

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