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1. Ru(II) Complexes with a Chemical and Redox-Active S ₂ N ₂ Ligand: Structures, Electrochemistry, and Metal–Ligand Cooperativity

   https://doi.org/10.1021/acs.organomet.7b00623  

   Durgaprasad, Gummadi; Luna, Javier A.; Spielvogel, Kyle D.; Haas, Christian; Shaw, Scott K.; Daly, Scott R. (October 2017, Organometallics)
2. Bisulfate as a redox-active ligand in vanadium-based electrocatalysis for CH ₄ functionalization

   https://doi.org/10.1039/D1CC06596C  

   Xiang, Danlei; Lin, Sheng-Chih; Deng, Jiao; Chen, Hao Ming; Liu, Chong (February 2022, Chemical Communications)

   The roles of unforgiving H 2 SO 4 solvent in CH 4 activation with molecular catalysts have not been experimentally well-illustrated despite computational predictions. Here, we provide experimental evidence that metal-bound bisulfate ligand introduced by H 2 SO 4 solvent is redox-active in vanadium-based electrocatalytic CH 4 activation discovered recently. Replacing one of the two terminal bisulfate ligands with redox-inert dihydrogen phosphate in the pre-catalyst vanadium (V)-oxo dimer completely quenches its activity towards CH 4 , which may inspire environmentally benign catalysis with minimal use of H 2 SO 4 . 

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3. Steric and electronic effects of ligand substitution on redox-active Fe ₄ S ₄ -based coordination polymers

   https://doi.org/10.1039/D1DT01652K  

   Salinas, Omar; Xie, Jiaze; Papoular, Robert J.; Horwitz, Noah E.; Elkaim, Erik; Filatov, Alexander S.; Anderson, John S. (January 2021, Dalton Transactions)

   null (Ed.)

   One of the notable advantages of molecular materials is the ability to precisely tune structure, properties, and function via molecular substitutions. While many studies have demonstrated this principle with classic carboxylate-based coordination polymers, there are comparatively fewer examples where systematic changes to sulfur-based coordination polymers have been investigated. Here we present such a study on 1D coordination chains of redox-active Fe 4 S 4 clusters linked by methylated 1,4-benzene-dithiolates. A series of new Fe 4 S 4 -based coordination polymers were synthesized with either 2,5-dimethyl-1,4-benzenedithiol (DMBDT) or 2,3,5,6-tetramethyl-1,4-benzenedithiol (TMBDT). The structures of these compounds have been characterized based on synchrotron X-ray powder diffraction while their chemical and physical properties have been characterized by techniques including X-ray photoelectron spectroscopy, cyclic voltammetry and UV–visible spectroscopy. Methylation results in the general trend of increasing electron-richness in the series, but the tetramethyl version exhibits unexpected properties arising from steric constraints. All these results highlight how substitutions on organic linkers can modulate electronic factors to fine-tune the electronic structures of metal–organic materials. 

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4. Influence of Multisite Metal–Ligand Cooperativity on the Redox Activity of Noninnocent N ₂ S ₂ Ligands

   https://doi.org/10.1021/acs.inorgchem.0c01353  

   Spielvogel, Kyle D.; Luna, Javier A.; Loria, Sydney M.; Weisburn, Leah P.; Stumme, Nathan C.; Ringenberg, Mark R.; Durgaprasad, Gummadi; Keith, Jason M.; Shaw, Scott K.; Daly, Scott R. (August 2020, Inorganic Chemistry)

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5. Sequential Deoxygenation of CO ₂ and NO ₂ ^– via Redox-Control of a Pyridinediimine Ligand with a Hemilabile Phosphine

   https://doi.org/10.1021/acs.inorgchem.3c02323  

   Lewine, Hanalei R.; Teigen, Allison G.; Trausch, April M.; Lindblom, Kaitlyn M.; Seda, Takele; Reinheimer, Eric W.; Kowalczyk, Tim; Gilbertson, John D. (September 2023, Inorganic Chemistry)