Zerovalent Triphosphine Ruthenium Complexes for Coupling Carbon Dioxide and Ethylene

IF 2.5 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Organometallics Pub Date : 2025-01-08 DOI:10.1021/acs.organomet.4c0043310.1021/acs.organomet.4c00433

Tristan T. Adamson, Laura G. Reeder, Steven P. Kelley and Wesley H. Bernskoetter*,

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引用次数: 0

Abstract

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 functionalization, 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 the 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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来源期刊

Organometallics 化学-无机化学与核化学

CiteScore

5.60

自引率

7.10%

发文量

382

审稿时长

1.7 months

期刊介绍： Organometallics is the flagship journal of organometallic chemistry and records progress in one of the most active fields of science, bridging organic and inorganic chemistry. The journal publishes Articles, Communications, Reviews, and Tutorials (instructional overviews) that depict research on the synthesis, structure, bonding, chemical reactivity, and reaction mechanisms for a variety of applications, including catalyst design and catalytic processes; main-group, transition-metal, and lanthanide and actinide metal chemistry; synthetic aspects of polymer science and materials science; and bioorganometallic chemistry.