Carboxylate Structural Effects on the Properties and Proton-Coupled Electron Transfer Reactivity of [CuO2CR]2+ Cores

Courtney E. Elwell, Mukunda Mandal, Caitlin J. Bouchey, Lawrence Que, Christopher J. Cramer, William B. Tolman

Research output: Contribution to journalArticle

Abstract

A series of complexes {[NBu4][LCuII(O2CR)] (R = -C6F5, -C6H4(NO2), -C6H5, -C6H4(OMe), -CH3, and -C6H2(iPr)3)} were characterized (with the complex R = -C6H4(m-Cl) having been published elsewhere (Mandal et al. J. Am. Chem. Soc. 2019, 141, 17236)). All feature N,N′,N″-coordination of the supporting L2- ligand, except for the complex with R = -C6H2(iPr)3, which exhibits N,N′,O-coordination. For the N,N′,N″-bound complexes, redox properties, UV-vis ligand-to-metal charge transfer (LMCT) features, and rates of hydrogen atom abstraction from 2,4,6,-tri-t-butylphenol using the oxidized, formally Cu(III) compounds LCuIII(O2CR) correlated well with the electron donating nature of R as measured both experimentally and computationally. Specifically, the greater the electron donation, the lower is the energy for LMCT and the slower is the reaction rate. The results are interpreted to support an oxidatively asynchronous proton-coupled electron transfer mechanism that is sensitive to the oxidative power of the [CuIII(O2CR)]2+ core.

Original languageEnglish (US)
Pages (from-to)15872-15879
Number of pages8
JournalInorganic Chemistry
Volume58
Issue number23
DOIs
StatePublished - Dec 2 2019

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carboxylates
Protons
electron transfer
reactivity
Ligands
ligands
protons
Electrons
Charge transfer
Metals
charge transfer
Catalyst supports
metals
Reaction rates
Hydrogen
hydrogen atoms
reaction kinetics
electrons
Atoms
energy

PubMed: MeSH publication types

  • Journal Article

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Carboxylate Structural Effects on the Properties and Proton-Coupled Electron Transfer Reactivity of [CuO2CR]2+ Cores. / Elwell, Courtney E.; Mandal, Mukunda; Bouchey, Caitlin J.; Que, Lawrence; Cramer, Christopher J.; Tolman, William B.

In: Inorganic Chemistry, Vol. 58, No. 23, 02.12.2019, p. 15872-15879.

Research output: Contribution to journalArticle

Elwell, Courtney E. ; Mandal, Mukunda ; Bouchey, Caitlin J. ; Que, Lawrence ; Cramer, Christopher J. ; Tolman, William B. / Carboxylate Structural Effects on the Properties and Proton-Coupled Electron Transfer Reactivity of [CuO2CR]2+ Cores. In: Inorganic Chemistry. 2019 ; Vol. 58, No. 23. pp. 15872-15879.
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