Redox-Active Tin(IV) Complexes Based on Sterically Hindered Catecholate Ligands

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The oxidative addition of sterically hindered 3,6-dicyclohexyl-o-benzoquinone (L1), 3,5-di-tert-octyl-o-benzoquinone (L2), 4-tert-octyl-o-benzoquinone (L3), and 3,5-bis(2-phenylpropyl)-o-benzoqui-none (L4) to tin(II) chloride in THF affords the corresponding tin(IV) catecholate complexes with the generalformula RCatSnCl2 · 2THF, where Cat is the catecholate fragment; and R is 3,6-с-Hex (I), 3,5-tert-Oct (II), 4-tert-Oct (III), and 3,5-C(Me)2 Ph (IV), regardless of the molar ratio of the starting reactants. The molecu-lar structures of substituted o-benzoquinone L4 and complexes I and III in the crystalline form are determined by X-ray diffraction (XRD) (CIF files CCDC nos. 2259370 (L4), 2259371 (I), and 2259372 (III)). The oxidation-reduction properties of synthesized compounds I–IV are studied by cyclic voltammetry.

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作者简介

S. Baryshnikova

Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences

编辑信件的主要联系方式.
Email: baryshnikova@iomc.ras.ru
俄罗斯联邦, Nizhny Novgorod

M. Arsen’eva

Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences

Email: baryshnikova@iomc.ras.ru
俄罗斯联邦, Nizhny Novgorod

N. Druzhkov

Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences

Email: baryshnikova@iomc.ras.ru
俄罗斯联邦, Nizhny Novgorod

G. Fukin

Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences

Email: baryshnikova@iomc.ras.ru
俄罗斯联邦, Nizhny Novgorod

E. Baranov

Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences

Email: baryshnikova@iomc.ras.ru
俄罗斯联邦, Nizhny Novgorod

A. Piskunov

Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences

Email: baryshnikova@iomc.ras.ru
俄罗斯联邦, Nizhny Novgorod

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2. Fig. 1. Structure of the A-benzoquinone L4 molecule (thermal ellipsoids of 30% probability are shown) a; b is a superposition of the structures of molecules A and B (green and blue bonds, respectively) of the L4 compound with thermal ellipsoids of atoms of 15% probability (hydrogen atoms are not shown).

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3. Fig. 2. Molecular structure of complexes I (a) and III (b, molecule A); superposition of structures of molecules A and B of complex III (green and blue bonds, respectively) (c). Thermal ellipsoids of 50% probability are shown. Hydrogen atoms are not shown.

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4. Fig. 3. CVA curves for complexes II and III (glassy carbon electrode, Ag/AgCl/KCl, 0.2 M [n-Bu4N]ClO4, CH2Cl2, c = 2 × 10-3 mol/l, V = 0.2 V/s, Ar).

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5. Scheme 1.

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6. Scheme 2.

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