Substituent and Isomer Effects on Structural, Spectroscopic, and Electrochemical Properties of Dirhodium(III,II) Complexes Containing Four Identical Unsymmetrical Bridging Ligands

详细信息    查看全文

• 作者：Karl M. Kadish ; Tuan D. Phan ; Lingamallu Giribabu ; Eric Van Caemelbecke ; and John L. Bear
• 刊名：Inorganic Chemistry
• 出版年：2003
• 出版时间：December 29, 2003
• 年：2003
• 卷：42
• 期：26
• 页码：8663 - 8673
• 全文大小：265K
• 年卷期：v.42,no.26(December 29, 2003)
• ISSN：1520-510X

文摘

Substituent and isomer effects on the structural, spectroscopic, (UV-visible and ESR) and electrochemical propertiesof dirhodium(III,II) complexes containing four identical unsymmetrical bridging ligands are reported for seven relatedcompounds of the type Rh₂(L)₄Cl where L = 2-(2-fluoroanilino)pyridinate (2-Fap), 2-(2,6-difluoroanilino)pyridinate(2,6-F₂ap), 2-(2,4,6-trifluoroanilino)pyridinate (2,4,6-F₃ap), or 2-(2,3,4,5,6-pentafluoroanilino)pyridinate (F₅ap) anion.Rh₂(2-Fap)₄Cl exists only in a (4,0) isomeric conformation while Rh₂(2,6-F₂ap)₄Cl, Rh₂(2,4,6-F₃ap)₄Cl, and Rh₂(F₅ap)₄Cl exist as both (4,0) and (3,1) isomers. It had earlier been demonstrated that Rh₂(L)₄Cl complexes canadopt different geometric conformations of the bridging ligands, but the current study provides the first examplewhere two geometric isomers of Rh₂⁵⁺ complexes are obtained for one compound using the same synthetic procedure.The synthesis, structural, spectroscopic, and/or electrochemical properties of (3,1) Rh₂(2,6-F₂ap)₄CN and (4,0)Rh₂(2,4,6-F₃ap)₄(CC)₂Si(CH₃)₃ are also reported and the data on these compounds is discussed in light of theirparent complexes, (3,1) Rh₂(2,6-F₂ap)₄Cl and (4,0) Rh₂(2,4,6-F₃ap)₄Cl.