Journal article
Influence of Multisite Metal–Ligand Cooperativity on the Redox Activity of Noninnocent N2S2 Ligands
Inorganic chemistry, Vol.59(15), pp.10845-10853
08/03/2020
DOI: 10.1021/acs.inorgchem.0c01353
PMID: 32639726
Abstract
Metal–ligand cooperativity (MLC) relies on chemically reactive ligands to assist metals with small-molecule binding and activation, and it has facilitated unprecedented examples of catalysis with metal complexes. Despite growing interest in combining ligand-centered chemical and redox reactions for chemical transformations, there are few studies demonstrating how chemically engaging redox active ligands in MLC affects their electrochemical properties when bound to metals. Here we report stepwise changes in the redox activity of model Ru complexes as zero, one, and two BH3 molecules undergo MLC binding with a triaryl noninnocent N2S2 ligand derived from o-phenylenediamine (L1). A similar series of Ru complexes with a diaryl N2S2 ligand with ethylene substituted in place of phenylene (L2) is also described to evaluate the influence of the o-phenylenediamine subunit on redox activity and MLC. Cyclic voltammetry (CV) studies and density functional theory (DFT) calculations show that MLC attenuates ligand-centered redox activity in both series of complexes, but electron transfer is still achieved when only one of the two redox-active sites on the ligands is chemically engaged. The results demonstrate how incorporating more than one multifunctional reactive site could be an effective strategy for maintaining redox noninnocence in ligands that are also chemically reactive and competent for MLC.
Details
- Title: Subtitle
- Influence of Multisite Metal–Ligand Cooperativity on the Redox Activity of Noninnocent N2S2 Ligands
- Creators
- Kyle D Spielvogel - Department of ChemistryJavier A Luna - Department of ChemistrySydney M Loria - Department of ChemistryLeah P Weisburn - Department of ChemistryNathan C Stumme - Department of ChemistryMark R Ringenberg - Institut für Anorganische ChemieGummadi Durgaprasad - Department of ChemistryJason M Keith - Department of ChemistryScott K Shaw - Department of ChemistryScott R Daly - Department of Chemistry
- Resource Type
- Journal article
- Publication Details
- Inorganic chemistry, Vol.59(15), pp.10845-10853
- Publisher
- American Chemical Society
- DOI
- 10.1021/acs.inorgchem.0c01353
- PMID
- 32639726
- ISSN
- 0020-1669
- eISSN
- 1520-510X
- Grant note
- DOI: 10.13039/100000165, name: Division of Chemistry, award: 1650894, 1651381
- Language
- English
- Date published
- 08/03/2020
- Academic Unit
- Chemistry
- Record Identifier
- 9984216605602771
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