Journal article
Sulfur-Containing Analogues of the Reactive [CuOH](2+) Core
Inorganic chemistry, Vol.60(7), pp.5217-5223
04/05/2021
DOI: 10.1021/acs.inorgchem.1c00216
PMCID: PMC8094167
PMID: 33733755
Abstract
With the aim of drawing comparisons to the highly reactive complex LCuOH (L = bis( 2,6-diisopropylphenylcarboxamido)pyridine), the complexes [Bu4N][LCuSR] (R = H or Ph) were prepared, characterized by spectroscopy and X- ray crystallography, and oxidized at low temperature to generate the species assigned as LCuSR on the basis of spectroscopy and theory. Consistent with the smaller electronegativity of S versus O, redox potentials for the LCuSR-/0 couples were similar to 50 mV lower than for LCuOH-/0, and the rates of the proton-coupled electron transfer reactions of LCuSR with anhydrous 1-hydroxy-2,2,6,6-tetramethyl-piperidine at -80 degrees C were significantly slower (by more than 100 times) than the same reaction of LCuOH. Density functional theory (DFT) and time-dependent DFT calculations on LCuZ (Z = OH, SH, SPh) revealed subtle differences in structural and UV-visible parameters. Further comparison to complexes with Z = F, Cl, and Br using complete active space (CAS) self-consistent field and localized orbital CAS configuration interaction calculations along with a valence-bond-like interpretation of the wave functions showed differences with previously reported results (J. Am. Chem. Soc. 2020, 142, 8514), and argue for a consistent electronic structure across the entire series of complexes, rather than a change in the nature of the ligand field arrangement for Z = F.
Details
- Title: Subtitle
- Sulfur-Containing Analogues of the Reactive [CuOH](2+) Core
- Creators
- Wen Wu - Washington University in St. LouisJacqui Tehranchi De Hont - University of MinnesotaRiffat Parveen - University of South DakotaBess Vlaisavljevich - University of South DakotaWilliam B. Tolman - Washington University in St. Louis
- Resource Type
- Journal article
- Publication Details
- Inorganic chemistry, Vol.60(7), pp.5217-5223
- DOI
- 10.1021/acs.inorgchem.1c00216
- PMID
- 33733755
- PMCID
- PMC8094167
- NLM abbreviation
- Inorg Chem
- ISSN
- 0020-1669
- eISSN
- 1520-510X
- Publisher
- Amer Chemical Soc
- Number of pages
- 7
- Grant note
- OAC-1626516 / NSF; National Science Foundation (NSF) GM47365 / National Institutes of Health; United States Department of Health & Human Services; National Institutes of Health (NIH) - USA CHE-1827756 / NSF-MRI Award; National Science Foundation (NSF); NSF - Office of the Director (OD)
- Language
- English
- Date published
- 04/05/2021
- Academic Unit
- Chemistry
- Record Identifier
- 9984618527802771
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