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...

Full description

Saved in:
Bibliographic Details
Main Authors: Comba, Peter (Author) , Grimm, Laura (Author) , Orvig, Chris (Author) , Rück, Katharina (Author) , Wadepohl, Hubert (Author)
Format: Article (Journal)
Language:English
Published: December 6, 2016
In: Inorganic chemistry
Year: 2016, Volume: 55, Issue: 24, Pages: 12531-12543
ISSN:1520-510X
DOI:10.1021/acs.inorgchem.6b01787
Online Access:Verlag, lizenzpflichtig, Volltext: https://doi.org/10.1021/acs.inorgchem.6b01787
Get full text
Author Notes:Peter Comba, Laura Grimm, Chris Orvig, Katharina Rück and Hubert Wadepohl
Description
Summary: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.
Item Description:Gesehen am 04.05.2020
Physical Description:Online Resource
ISSN:1520-510X
DOI:10.1021/acs.inorgchem.6b01787