Influence of the Eliminated Ligand Structure on the Reduction Rate of the Cobalt(III) Complexes

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Abstract

The reduction of the heteroleptic cobalt(III) complexes with bipyridine ligands of different structures of the model drug molecule is studied by in situ NMR spectroscopy. The nature of the ligand eliminated during reduction is shown to exert a substantial effect on the reduction rate, which indicates that an optimum amount of cobalt should be chosen for the redox-activated delivery of a certain drug.

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About the authors

I. A. Nikovskii

Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences

Email: khakina90@ineos.ac.ru
Russian Federation, Moscow

K. A. Spiridonov

Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences; Moscow State University

Email: khakina90@ineos.ac.ru
Russian Federation, Moscow; Moscow

A. A. Dan′shina

Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences; Moscow Institute of Physics and Technology (National Research University)

Email: khakina90@ineos.ac.ru
Russian Federation, Moscow; Dolgoprudnyi

E. A. Khakina

Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences

Author for correspondence.
Email: khakina90@ineos.ac.ru
Russian Federation, Moscow

Yu. V. Nelyubina

Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences

Email: khakina90@ineos.ac.ru
Russian Federation, Moscow

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2. Fig. 1. General view of complex II, illustrating the coordination environment of the cobalt(III) ion. Here and further, perchlorate anions are not shown, and non-hydrogen atoms are represented as ellipsoids of thermal vibrations (p = 30%). The numbering is given only for the metal ion and symmetrically independent heteroatoms.

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3. Fig. 2. Fragment of the crystal packing of complex II, illustrating the formation of 1D chains due to the stacking interaction between bipyridine ligands (highlighted in pink).

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4. Fig. 3. Dynamics of changes in the 1H NMR spectrum over time during the reduction of complex II with ascorbic acid in an argon atmosphere (the spectrum was recorded in a mixture of acetonitrile-d3 and deuterated water, 4:1 vol.).

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5. Fig. 4. Comparison of the paramagnetic regions of the NMR spectra of the [Co(Bipy)3]ClO4 complex (top) and reduction products I (center) and II (bottom).

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6. Fig. 5. Comparison of the mass spectra of the reduction products of complexes I (a) and II (b).

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7. Fig. 6. Kinetic curves of the consumption of complexes I and II during the reduction of ascorbic acid in an argon atmosphere.

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8. Fig. 7. Dependence of the logarithms of the concentration of ln[C] complexes I and II on the reaction time during reduction with ascorbic acid in an argon atmosphere.

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9. Scheme 1.

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10. Scheme 2.

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