Binuclear Diphenyltin(IV) Complexes with Salicylaldimine Ligands. Synthesis, Structure, Electrochemical Properties

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Resumo

New binuclear tin(IV) complexes based on salicylic Schiff bases and diphenyltin oxide Ph2SnO were obtained. The structures of the complexes were confirmed by 1H, 13C and 119Sn NMR spectroscopy and X-ray diffraction analysis (CCDC 2433411). UV-Vis spectroscopy of complexes 1–4 showed that a bathochromic shift of all ligand absorption bands was observed upon complexation with the metal fragment. The ability of complexes 1–4 to undergo electrochemical transformations was investigated by cyclic voltammetry. In all cases, the oxidation and reduction of the complexes are irreversible. In the cases of complexes 2–4 with a conjugated bridge, the oxidation of two metal fragments occurs at one potential, whereas complex 1 with an unconjugated adipic bridge has two peaks on the oxidation curve at different potentials, which is probably since the oxidation of two different ‘ends’ of the molecule occurs at different potentials.

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Sobre autores

V. Klok

Zelinsky Institute of Organic Chemistry Russian Academy of Sciences Moscow

Email: en@ioc.ac.ru
Rússia, Moscow, 119991

P. Shangin

Zelinsky Institute of Organic Chemistry Russian Academy of Sciences Moscow

Email: en@ioc.ac.ru
Rússia, Moscow, 119991

I. Krylova

Zelinsky Institute of Organic Chemistry Russian Academy of Sciences Moscow

Email: en@ioc.ac.ru
Rússia, Moscow, 119991

M. Minyaev

Zelinsky Institute of Organic Chemistry Russian Academy of Sciences Moscow

Email: en@ioc.ac.ru
Rússia, Moscow, 119991

M. Syroeshkin

Zelinsky Institute of Organic Chemistry Russian Academy of Sciences Moscow

Email: en@ioc.ac.ru
Rússia, Moscow, 119991

V. Pechennikov

First Moscow State Medical University

Email: en@ioc.ac.ru
Rússia, Moscow, 119048

M. Egorov

Zelinsky Institute of Organic Chemistry Russian Academy of Sciences Moscow

Email: en@ioc.ac.ru
Rússia, Moscow, 119991

E. Nikolaevskaya

Zelinsky Institute of Organic Chemistry Russian Academy of Sciences Moscow

Autor responsável pela correspondência
Email: en@ioc.ac.ru
Rússia, Moscow, 119991

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2. Scheme 1. Synthesis of complexes I–IV using ligands L¹–L⁴.

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3. Fig. 1. Molecular structure of complex III. Hydrogen atoms are not shown. Selected bond lengths (Å): Sn(1)–O(1) 2.0755(19), Sn(1)–O(2) 2.1307(17), Sn(1)–N(1) 2.163(2), Sn(2)–O(3) 2.0723(18), Sn(2)–O(4) 2.1281(17), Sn(2)–N(3) 2.175(2), N(1)–C(1) 1.299(4), N(1)–N(2) 1.392(3), N(2)–C(20) 1.308(4), N(3)–N(4) 1.396(3), N(3)–C(28) 1.293(3), N(4)–C(27) 1.315(3).

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4. Fig. 2. Ultraviolet spectra of complexes I (a) and II (b) (5 × 10⁻⁵ M) and the starting ligands L¹ and L² (2.5 × 10⁻⁵ M) in DMF.

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5. Fig. 3. Ultraviolet spectra of complexes III (a) and IV (b) (4 × 10⁻⁵ M) and the initial ligands L³ and L⁴ (1 × 10⁻⁴ M) in DMF.

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6. Fig. 4. CVA curves of complex I and the initial ligand L¹. Concentration 2.5 mM in 0.1 M NBu₄PF₆/DMF, potential values ​​are given relative to the Fc/Fc⁺ pair, potential scan rate 0.1 V s⁻¹. a) reduction; b) oxidation.

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7. Fig. 4. CVA curves of complex I and the initial ligand L¹. Concentration 2.5 mM in 0.1 M NBu₄PF₆/DMF, potential values ​​are given relative to the Fc/Fc⁺ pair, potential scan rate 0.1 V s⁻¹. a) reduction; b) oxidation.

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8. Fig. 5. CVA curves of complex II and the initial ligand L². Concentration 2.5 mM in 0.1 M NBu₄PF₆/DMF, potential values ​​are given relative to the Fc/Fc⁺ pair, potential scan rate 0.1 V s⁻¹. a) reduction; b) oxidation.

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9. Fig. 6. CVA curves of complex III and the initial ligand L³. Concentration 2.5 mM in 0.1 M NBu₄PF₆/DMF, potential values ​​are given relative to the Fc/Fc⁺ pair, potential scan rate 0.1 V s⁻¹. a) reduction; b) oxidation.

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10. Fig. 7. CVA curves of complex IV and the initial ligand L⁴. Concentration 2.5 mM in 0.1 M NBu₄PF₆/DMF, potential values ​​are given relative to the Fc/Fc⁺ pair, potential scan rate 0.1 V s⁻¹. a) reduction; b) oxidation.

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11. Fig. 8. CVA curves of complex IV reduction at different potential scan rates (0.1–1 V s⁻¹). Concentration 2.5 mM in 0.1 M NBu₄PF₆/DMF, potentials are given relative to the Fc/Fc⁺ pair.

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