Anthony N. Micci, Julia E. Fumo, Robert D. Pike and Davide Lionetti*,
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引用次数: 0
摘要
在配位溶剂中,三芳基膦配体支持的钌-烯催化剂中电子转移(ET)的结果尚未完全阐明,众所周知,在氧化过程中,类似的 Ru 物种会发生进一步的转化,并可能揭示这些化合物的新反应模式。在此,我们报告了含有取代三芳基膦(PArX3)的 (p-cymene)RuCl2(PArX3) 复合物的电化学研究以及配体取代基对 ET 过程的影响。这些配合物在取决于配体取代基 (X) 的电位下发生 ET;在 CH3CN 中,电化学氧化会产生新的产物,其形成和 ET 行为也取决于这些取代基。根据在这些转化过程中失去亚甲基的证据,这些反应的产物被配制成三(腈)络合物 (PArX3)RuCl2(NCCH3)3 。
Effects of Substituted Triarylphosphine Ligands on Electron Transfer in [(p-Cymene)Ru] Complexes
The consequences of electron transfer (ET) in ruthenium-arene catalysts supported by triarylphosphine ligands have not been fully elucidated in coordinating solvents, which are known to engender further transformations in analogous Ru species upon oxidation and may reveal new modes of reactivity in these compounds. Herein, we report electrochemical studies of (p-cymene)RuCl2(PArX3) complexes containing substituted triarylphosphines (PArX3) and the effects of the ligand substituents on ET processes. These complexes undergo ET at potentials that depend on the ligand substituents (X); in CH3CN, electrochemical oxidation generates new products whose formation and ET behavior also depend on these substituents. Based on evidence for loss of cymene in these transformations, the products of these reactions are formulated as the tris(nitrile) complexes (PArX3)RuCl2(NCCH3)3.
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.