Journal article
The Influence of Redox-Innocent Donor Groups in Tetradentate Ligands Derived from o -Phenylenediamine: Electronic Structure Investigations with Nickel
Inorganic chemistry, Vol.58(19), pp.12756-12774
09/06/2019
DOI: 10.1021/acs.inorgchem.9b01675
PMID: 31490065
Abstract
The continued development of redox-active ligands requires an understanding as to how ligand modifications and related factors affect the locus of redox activity and spin density in metal complexes. Here we describe the synthesis, characterization, and electronic structure of nickel complexes containing triaryl NNNN (
) and SNNS (
) ligands derived from
-phenylenediamine. The tetradentate ligands in
and
were investigated and compared to those in metal complexes with compositionally similar ligands to determine how ligand-centered redox properties change when redox-active flanking groups are replaced with redox-innocent NMe
or SMe. A derivative of
in which the phenylene backbone was replaced with ethylene (
) was also prepared to interrogate the importance of
-phenylenediamine for ligand-centered redox activity. Cyclic voltammograms collected for
and
revealed two fully reversible ligand-centered redox events. Remarkably, several quasi-reversible ligand-centered redox waves were also observed for
despite the absence of the
-phenylenediamine subunit. Oxidizing
and
with silver salts containing different counteranions (BF
, OTf
, NTf
) allowed the electrochemically generated complexes to be analyzed as a function of different oxidation states using single-crystal X-ray diffraction (XRD), EPR spectroscopy, and S K-edge X-ray absorption spectroscopy. The experimental data are corroborated by DFT calculations, and together, they reveal how the location of unpaired spin density and electronic structure in singly and doubly oxidized salts of
and
varies depending on the coordinating ability of the counteranions and exogenous ligands such as pyridine.
Details
- Title: Subtitle
- The Influence of Redox-Innocent Donor Groups in Tetradentate Ligands Derived from o -Phenylenediamine: Electronic Structure Investigations with Nickel
- Creators
- Kyle D Spielvogel - Department of Chemistry , The University of Iowa , E331 Chemistry Building , Iowa City , Iowa 52242-1294 , United StatesEzra J Coughlin - H.C. Brown Laboratory, Department of Chemistry , Purdue University , West Lafayette , Indiana 47907 , United StatesHayley Petras - Department of Chemistry , The University of Iowa , E331 Chemistry Building , Iowa City , Iowa 52242-1294 , United StatesJavier A Luna - Department of Chemistry , The University of Iowa , E331 Chemistry Building , Iowa City , Iowa 52242-1294 , United StatesAustin Benson - Department of Chemistry , The University of Iowa , E331 Chemistry Building , Iowa City , Iowa 52242-1294 , United StatesCourtney M Donahue - Department of Chemistry , The University of Iowa , E331 Chemistry Building , Iowa City , Iowa 52242-1294 , United StatesAmani Kibasa - Department of Chemistry , The University of Iowa , E331 Chemistry Building , Iowa City , Iowa 52242-1294 , United StatesKyounghoon Lee - Department of Chemistry , The University of Iowa , E331 Chemistry Building , Iowa City , Iowa 52242-1294 , United StatesRyan Salacinski - Department of Chemistry , The University of Iowa , E331 Chemistry Building , Iowa City , Iowa 52242-1294 , United StatesSuzanne C Bart - H.C. Brown Laboratory, Department of Chemistry , Purdue University , West Lafayette , Indiana 47907 , United StatesScott K Shaw - Department of Chemistry , The University of Iowa , E331 Chemistry Building , Iowa City , Iowa 52242-1294 , United StatesJames J Shepherd - Department of Chemistry , The University of Iowa , E331 Chemistry Building , Iowa City , Iowa 52242-1294 , United StatesScott R Daly - Department of Chemistry , The University of Iowa , E331 Chemistry Building , Iowa City , Iowa 52242-1294 , United States
- Resource Type
- Journal article
- Publication Details
- Inorganic chemistry, Vol.58(19), pp.12756-12774
- Publisher
- United States
- DOI
- 10.1021/acs.inorgchem.9b01675
- PMID
- 31490065
- ISSN
- 0020-1669
- eISSN
- 1520-510X
- Grant note
- DOI: 10.13039/100000165, name: Division of Chemistry, award: 1650894, 1651381; DOI: 10.13039/100000138, name: U.S. Department of Education
- Language
- English
- Date published
- 09/06/2019
- Academic Unit
- Chemistry
- Record Identifier
- 9984001174802771
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