Synthesis and coordination chemistry of hexadentate picolinic acid based bispidine ligands

• Verfasst von: Comba, Peter [VerfasserIn]
• Verfasst von: Grimm, Laura [VerfasserIn]
• Verfasst von: Orvig, Chris [VerfasserIn]
• Verfasst von: Rück, Katharina [VerfasserIn]
• Verfasst von: Wadepohl, Hubert [VerfasserIn]
• Titel: Synthesis and coordination chemistry of hexadentate picolinic acid based bispidine ligands
• Verf.angabe: Peter Comba, Laura Grimm, Chris Orvig, Katharina Rück and Hubert Wadepohl
• E-Jahr: 2016
• Jahr: December 6, 2016
• Umfang: 13 S.
• Teil: volume:55
• Teil: year:2016
• Teil: number:24
• Teil: pages:12531-12543
• Teil: extent:13
• Fussnoten: Gesehen am 04.05.2020
• Titel Quelle: Enthalten in: Inorganic chemistry
• Ort Quelle: Washington, DC : American Chemical Society, 1962
• Jahr Quelle: 2016
• Band/Heft Quelle: 55(2016), 24, Seite 12531-12543
• ISSN Quelle: 1520-510X
• DOI: doi:10.1021/acs.inorgchem.6b01787
• Datenträger: Online-Ressource
• Sprache: eng
• K10plus-PPN: 1697044255

Abstract

The synthesis and CuII, NiII, ZnII, CoII, and GaIII coordination chemistry of the two isomeric hexadentate N5O ligands 6-[[9-hydroxy-1,5-bis(methoxycarbonyl)-7-methyl-6,8-bis(pyridin-2-yl)-3,7-diazabicyclo[3.3.1]nonan-3-yl]methyl]picolinic acid (Hbispa1a) and 6-[[9-hydroxy-1,5-bis(methoxycarbonyl)-7-methyl-2,4-bis(pyridin-2-yl)-3,7-diazabicyclo[3.3.1]nonan-3-yl]methyl]picolinic acid (Hbispa1b), picolinic acid-appended bispidines, are described. The two ligands are highly preorganized for octahedral coordination geometries and are particularly well suited for tetragonal symmetries, i.e., for Jahn-Teller labile ground states. This is confirmed by all data presented: solid-state structures, solution spectroscopy, electrochemistry, and CuII complex stabilities. Differences in the preorganization of the two isomers for the Jahn-Teller labile CuII centers are thoroughly analyzed on the basis of the crystal structures and an angular-overlap-model-based ligand-field analysis.