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Exceptional Manganese(II) Stability and Manganese(II)/Zinc(II) Selectivity with Rigid Polydentate Ligands.


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 H 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.

SUBMITTER: Cieslik P 

PROVIDER: S-EPMC9305554 | biostudies-literature | 2022 Mar

REPOSITORIES: biostudies-literature

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Exceptional Manganese(II) Stability and Manganese(II)/Zinc(II) Selectivity with Rigid Polydentate Ligands.

Cieslik Patrick P   Comba Peter P   Dittmar Benedikt B   Ndiaye Daouda D   Tóth Éva É   Velmurugan Gunasekaran G   Wadepohl Hubert H  

Angewandte Chemie (International ed. in English) 20220120 10


While Mn<sup>II</sup> complexes meet increasing interest in biomedical applications, ligands are lacking that enable high Mn<sup>II</sup> complex stability and selectivity vs. Zn<sup>II</sup> , 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 Mn<sup>II</sup> , yielding eight-coordinate Mn<sup>II</sup> complexes with record stabilities. In contrast, the smaller Zn<sup>II</sup  ...[more]

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