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• W3040755432 endingPage "10853" @default.
• W3040755432 startingPage "10845" @default.
• W3040755432 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." @default.
• W3040755432 created "2020-07-16" @default.
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• W3040755432 date "2020-07-08" @default.
• W3040755432 modified "2023-10-14" @default.
• W3040755432 title "Influence of Multisite Metal–Ligand Cooperativity on the Redox Activity of Noninnocent N₂S₂ Ligands" @default.
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• W3040755432 doi "https://doi.org/10.1021/acs.inorgchem.0c01353" @default.
• W3040755432 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/32639726" @default.
• W3040755432 hasPublicationYear "2020" @default.
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