Synthesis and coordination chemistry of hexadentate picolinic acid based bispidine ligands

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...

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Hauptverfasser: Comba, Peter (VerfasserIn) , Grimm, Laura (VerfasserIn) , Orvig, Chris (VerfasserIn) , Rück, Katharina (VerfasserIn) , Wadepohl, Hubert (VerfasserIn)
Dokumenttyp: Article (Journal)
Sprache:Englisch
Veröffentlicht: December 6, 2016
In: Inorganic chemistry
Year: 2016, Jahrgang: 55, Heft: 24, Pages: 12531-12543
ISSN:1520-510X
DOI:10.1021/acs.inorgchem.6b01787
Online-Zugang:Verlag, lizenzpflichtig, Volltext: https://doi.org/10.1021/acs.inorgchem.6b01787
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Verfasserangaben:Peter Comba, Laura Grimm, Chris Orvig, Katharina Rück and Hubert Wadepohl
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Zusammenfassung: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.
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Beschreibung:Online Resource
ISSN:1520-510X
DOI:10.1021/acs.inorgchem.6b01787