Hexaethyltripyrrindione (H₃Et₆tpd): A Non-Innocent Ligand Forming Stable Radical Complexes with Divalent Transition-Metal Ions

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• 作者：Stefanie Bahnmü ; ller ; Jacqueline Plotzitzka ; Dirk Baabe ; Birte Cordes ; Dirk Menzel ; Katharina Schartz ; Peter Schweyen ; Richard Wicht and Martin Brö ; ring
• 刊名：European Journal of Inorganic Chemistry
• 出版年：2016
• 出版时间：October 2016
• 年：2016
• 卷：2016
• 期：29
• 页码：4761-4768
• 全文大小：1812K
• ISSN：1099-0682c

文摘

Nickel, palladium, and copper complexes of the tripyrrolic ligand hexaethyltripyrrindione (H₃Et₆tpd, 1) have been prepared and characterized by UV/Vis and EPR spectroscopy, as well as by single-crystal X-ray structure determination. In all cases the metal ion is coordinated in a distorted square-planar geometry carrying a water ligand at the fourth coordination site. The Et₆tpd ligand acts as a radical dianion in all cases. In solution, monomeric species are present in which the open-shell character of the ligand becomes apparent through EPR spectroscopic measurements. In the solid state, the compounds form polymorphs with tightly bonded π–π dimers and chains showing small interplanar distances of 3.191–3.493 Å to one or more neighboring molecules. Magnetic measurements on the complexes confirmed the radical character of the tripyrrindione ligand and revealed strong intermolecular magnetic interactions in these complexes.