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1. Zerovalent Triphosphine Ruthenium Complexes for Coupling Carbon Dioxide and Ethylene

   https://doi.org/10.1021/acs.organomet.4c00433  

   Adamson, Tristan T; Reeder, Laura G; Kelley, Steven P; Bernskoetter, Wesley H (January 2025, Organometallics)

   The coupling of carbon dioxide and ethylene to generate value added chemicals has been part of recent fundamental advances to improve sustainability in commercial chemical synthons. A formal zerovalent triphosphine ligated ruthenium complex, (tBuP(CH2CH2PEt2)2)Ru(κ-S-DMSO)(C2H4), was found to promote CO2 activation, affording products derived from both a 1:1 and 1:2 ethylene to CO2 coupling stoichiometry. The equimolecular coupling reaction selectively afforded a five-membered ruthenium lactone species, (tBuP(CH2CH2PEt2)2)Ru(κ-S-DMSO)(κ-C,κ-O-CH2CH2CO2), under low CO2 pressure. At higher CO2 pressure, the ruthenium lactone complex activated a second equivalent of CO2, yielding a dimeric methylmalonate ruthenium compound, [(tBuP(CH2CH2PEt2)2)Ru(μ2, κ1-O, κ2-O,O-O2CCHCH3CO2)]2. Both carbon dioxide activation products were characterized by X-ray diffraction. Preliminary mechanistic studies suggest that reversible β-H elimination is a key process in conversion between the two ruthenium carboxylate species. A rare formally zerovalent ruthenium coordination compound stabilized only by ethylene and DMSO ligands was also isolated and characterized. 

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2. Dinuclear nitrido-bridged osmium complexes inhibit the mitochondrial calcium uniporter and protect cortical neurons against lethal oxygen–glucose deprivation

   https://doi.org/10.1039/d2cb00189f  

   Woods, Joshua J.; Novorolsky, Robyn J.; Bigham, Nicholas P.; Robertson, George S.; Wilson, Justin J. (January 2023, RSC Chemical Biology)

   We have investigated the biological properties of the osmium analogue of a potent ruthenium-based mitochondrial calcium uniporter inhibitor and have found it to possess distinct properties. 

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3. Electrocatalytic conversion of biomass-derived oxygenated aromatics to cycloalkanes

   https://doi.org/10.1039/D4SE01149J  

   Kasad, Meheryar R; Jackson, James E; Saffron, Christopher M (December 2024, Sustainable Energy & Fuels)

   Electrocatalytic transformation of oxygenated aromatics to cycloalkanes on activated carbon cloth-supported ruthenium and platinum under mild conditions (≤60°, atmospheric pressure) using hydrogen equivalents producedin situby water splitting. 

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4. Autocatalytic Activation of a Ruthenium-PNN-Pincer Hydrogenation Catalyst

   https://doi.org/10.1021/acscatal.4c04475  

   Perez, Jose_Fernando Carbajal; Kirlin, Fallyn L; Reynolds, Eamon F; Altomare-Jarczyk, Cole E; Joseph, Benjamin T; Keith, Jason M; Chianese, Anthony R (November 2024, ACS Catalysis)

   Maseras, Feliu (Ed.)

   In this article, we describe a detailed experimental and computational study of the activation mechanism for a highly active PNN-pincer ruthenium(0) pre-catalyst for the hydrogenation of polar organic compounds. The pre-catalyst activates by reaction with two equivalents of hydrogen, resulting in a net oxidative addition to ruthenium and hydrogenation of an imine functional group on the supporting ligand. The kinetics of pre-catalyst hydrogenation were measured by UV-visible spectroscopy under catalytically relevant conditions (10-39 bar hydrogen, 298 K). The kinetic data, in combination with density functional theory calculations, support an intriguing autocatalytic mechanism, where the product ruthenium(II) complex catalyzes the hydrogenation of the ruthenium(0) pre-catalyst. 

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5. Red-shifted activity-based sensors for ethylene via direct conjugation of fluorophore to metal–carbene

   https://doi.org/10.1039/D3CB00079F  

   Dacon, Nicholas J.; Wu, Nathan B.; Michel, Brian W. (November 2023, RSC Chemical Biology)

   Direction conjugation of a BODIPY fluorophore with the chelating ruthenium ligand result in red-shifted ethylene probes Con-BEP-4 and Con-BEP-5. Synthesis, photophysical properties, and live cell imaging studies are reported. 

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