Exceptional Manganese(II) Stability and Manganese(II)/Zinc(II) Selectivity with Rigid Polydentate Ligands.
Angew Chem Int Ed Engl
; 61(10): e202115580, 2022 Mar 01.
Article
en En
| MEDLINE
| ID: mdl-34979049
ABSTRACT
While MnII complexes meet increasing interest in biomedical applications, ligands are lacking that enable high MnII complex stability and selectivity vs. ZnII , the most relevant biological competitor. We report here two new bispidine derivatives, which provide rigid and large coordination cavities that perfectly match the size of MnII , yielding eight-coordinate MnII complexes with record stabilities. In contrast, the smaller ZnII ion cannot accommodate all ligand donors, resulting in highly strained and less stable six-coordinate complexes. Combined theoretical and experimental data (X-ray crystallography, potentiometry, relaxometry and 1 Hâ
NMR spectroscopy) demonstrate unprecedented selectivity for MnII vs. ZnII (KMnL /KZnL of 108 -1010 ), in sharp contrast to the usual Irving-Williams behavior, and record MnII complex stabilities and inertness with logKMnL close to 25.
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Colección:
01-internacional
Base de datos:
MEDLINE
Idioma:
En
Revista:
Angew Chem Int Ed Engl
Año:
2022
Tipo del documento:
Article
País de afiliación:
Alemania