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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.more » « lessFree, publicly-accessible full text available January 27, 2026
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Adamson, Tristan T.; Uttley, Katherine B.; Kelley, Steven P.; Bernskoetter, Wesley H. (, Organometallics)
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Adamson, Tristan T.; Kelley, Steven P.; Bernskoetter, Wesley H. (, Organometallics)
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