Rational Synthesis of Heteroleptic Tris(chelate) Ruthenium Complexes [RuII(2-Ph-2鈥?Py)(LL)(L鈥?sup>L鈥?]PF6 by Selective Substitution of the Ligand Trans to the Ru

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• 作者：Bastien Boff ; Moussa Ali ; Larissa Alexandrova ; Noel 脕ngel Espinosa-Jalapa ; Rafael Omar Saavedra-D铆az ; Ronan Le Lagadec ; Michel Pfeffer
• 刊名：Organometallics
• 出版年：2013
• 出版时间：September 23, 2013
• 年：2013
• 卷：32
• 期：18
• 页码：5092-5097
• 全文大小：286K
• 年卷期：v.32,no.18(September 23, 2013)
• ISSN：1520-6041

文摘

[Ru(NN)(MeCN)₂(2-Ph-2鈥?Py)]PF₆ (2-Ph-2鈥?Py = ortho-metalated 2-phenylpyridine, NN = phenanthroline, 2,2鈥?bipyridine), in which one of the nitrogens of the NN ligand is bound to Ru trans to the phenyl unit of 2-PhPy, were slowly isomerized (2 days) in refluxing 1,1-dichloroethane/MeCN (9/1) or more rapidly (although with a reduced yield) in the presence of UV light, to afford compounds in which the same N atom was bound to Ru trans to the pyridine of 2-PhPy; these new compounds, in opposition to their well-known isomers, proved to be nicely reactive toward substitution reactions of the MeCN ligands, by other bidentate N-containing ligands such as 4,4鈥?R₂-2,2鈥?bipyridine (R = H, OMe, COOH) and 4,7-dimethyl-1,10-phenanthroline. These results question the exact structure of the already reported heteroleptic tris(chelate) Ru^II complexes obtained from the same starting material in which the incoming bidentate ligands were incorrectly believed to be bound to the Ru atom at positions trans to N atoms.