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Ferrocene-Containing Tin(IV) Complexes Based on o‑Benzoquinone and o‑Iminobenzoquinone Ligands. Synthesis, Molecular Structure, and Electrochemical Properties

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journal contribution
posted on 27.04.2020, 15:37 by Svetlana V. Baryshnikova, Andrey I. Poddel’sky, Ekaterina V. Bellan, Ivan V. Smolyaninov, Anton V. Cherkasov, Georgy K. Fukin, Nadezhda T. Berberova, Vladimir K. Cherkasov, Gleb A. Abakumov
The addition of different substituted o-benzoquinones and o-iminobenzoquinones to tin­(II) bis­(o-iminophenolates) of the types (Fc-IP)2SnII and (Fc-4,6-IP)2SnII (where Fc-IP is anion 2-(ferrocenylmethyleneamino)­phenolate [Fc-C­(H)N­(C6H4)­O] and Fc-4,6-IP is anion 2-(ferrocenylmethyleneamino)-4,6-di-tert-butylphenolate [Fc-C­(H)N­(4,6-tBu-C6H2)­O]) in tetrahydrofuran leads to the oxidation of Sn­(II) to Sn­(IV) with formation of the corresponding tin­(IV) catecholates (Fc-4,6-IP)2SnIV(3,6-Cat) (1), (Fc-IP)2SnIV(3,6-Cat) (2), (Fc-4,6-IP)2SnIV(4-Cl-3,6-Cat) (3), (Fc-IP)2SnIV(4-Cl-3,6-Cat) (4), (Fc-4,6-IP)2SnIV(4,5-Cl2-3,6-Cat) (5), and (Fc-IP)2SnIV(4,5-Cl2-3,6-Cat) (6) or the o-amidophenolates (Fc-4,6-IP)2SnIV(AP-Me) (7), (Fc-IP)2SnIV(AP-iPr) (8), and (Fc-4,6-IP)2SnIV(AP-iPr) (9). Here ligands 3,6-Cat, 4-Cl-3,6-Cat, and 4,5-Cl2-3,6-Cat are dianions 3,6-di-tert-butyl-, 4-chloro-3,6-di-tert-butyl-, and 4,5-dichloro-3,6-di-tert-butylcatecholates, respectively, and AP-Me and AP-iPr are dianions 4,6-di-tert-butyl-N-(2,6-dimethylphenyl)-o-amidophenolate and 4,6-di-tert-butyl-N-(2,6-diisopropylphenyl)-o-amidophenolate, respectively. Complexes 19 have been characterized in detail by IR spectroscopy, cyclic voltammetry, and 1H, 13C, and 119Sn NMR spectroscopy. The molecular structures of tin­(IV) complexes 5, 7, and 9 in the crystalline state were determined by single-crystal X-ray diffraction analysis. Complexes demonstrate a series of successive oxidations involving alternately catecholato/o-amidophenolato centers and ferrocenyl moieties. The relative oxidation potentials of these redox centers depend on the acceptor properties of the redox-active chelating O,O′ or O,N ligand. An increase in the acceptor properties of redox-active o-quinonato-type ligands leads to an increase in the oxidation potentials of redox ligands as well as the following oxidation of ferrocenyl group(s). In two series of complexes, (Fc-4,6-L)2SnL′ and (Fc-L)2SnL′, where L′ is AP-iPr, AP-Me, 3,6-Cat, 4-Cl-3,6-Cat, and 4,5-Cl2-3,6-Cat, a more pronounced convergence of the oxidation potentials of the redox-active o-quinonato ligand and ferrocenyl group occurs in the series (Fc-L)2SnL′.

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