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

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 1-9 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'.