| Title | Synthesis and Coordination Chemistry of Hexadentate Picolinic Acid Based Bispidine Ligands |
| Publication Type | Journal Article |
| Year of Publication | 2016 |
| Authors | Comba, P, Grimm, L, Orvig, C, Rück, K, Wadepohl, H |
| Journal | Inorg. Chem. |
| Volume | 55 |
| Pagination | 12531-12543 |
| Date Published | DEC 19 |
| Type of Article | Article |
| ISSN | 0020-1669 |
| Abstract | The synthesis and Cu-II, Ni-II, Zn-II, Co-II, and Ga-III coordination chemistry of the two isomeric hexadentate N5O ligands 6-{[}{[}9-hydroxy-1,5-bis(methoxycarbony1)-7-methyl-6,8-bis(pyridin-2-yl )-3,7-diazabicyclo{[}3.3.1]nonan-3-yl]methyl] picolinic acid (Hbispa(1a)) and 6-{[}{[}9-hydroxy-1,5-bis(methoxycarbony1)-7-methyl-2,4-bis(pyridin-2-yl )-3,7-diazabicyclo{[}3.3.1]nonan-3-yl]methyl]picolinic acid (Hbispa(1b)), 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 Cu-II centers are thoroughly analyzed on the basis of the crystal structures and an angular-overlap-model-based ligand-field analysis. |
| DOI | 10.1021/acs.inorgchem.6b01787 |
