Classification of the Electronic Properties of Chelating Ligands in cis-[LL′Rh(CO)2] Complexes

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• 作者：Yves Canac ; Christine Lepetit
• 刊名：Inorganic Chemistry
• 出版年：2017
• 出版时间：January 3, 2017
• 年：2017
• 卷：56
• 期：1
• 页码：667-675
• 全文大小：506K
• ISSN：1520-510X

文摘

By analogy to the Tolman electronic parameter, a ligand electronic parameter, referred to as L₂EP, is introduced here for estimating the donating ability of chelating ligands, featuring two coordinating extremities. It is based on the average of the computed infrared stretching frequencies of CO in a series of isostructural rhodium(I)-dicarbonyl complexes, that is linearly correlated to the number x of N-heterocyclic carbene coordinating ends (x = 0, 1, or 2). The L₂EP values allow the design of an unified scale for the classification of the electron donation of chelating ligands, based on an ortho-phenylene bridge substituted by two coordinating extremities, which may have a different donating character. Strengths and limitations of the L₂EP scale are illustrated for a large diversity of bidentate chelating ligands with coordinating ends ranging from extremely electron-rich phosphonium yldiides to extremely electron-poor amidiniophosphonites.