Binuclear Triphenylantimony(V) Catecholates through N-Donor Linkers: Structural Features and Redox Properties

A series of binuclear triphenylantimony(V) bis-catecholato complexes 1-11 of the type (Cat)Ph₃Sb-linker-SbPh₃(Cat) was prepared by a reaction of the corresponding mononuclear catecholates (Cat)SbPh₃ with a neutral bidentate donor linker ligands pyrazine (Pyr), 4,4'-dipyridyl (Bipy), bis-(pyridine-4-yl)-disulfide (PySSPy), and diazobicyclo[2,2,2]octane (DABCO) in a dry toluene: Cat = 3,6-di-tert-butyl-catecholate (3,6-DBCat), linker = Pyr (1); PySSPy (2); Bipy (3); DABCO (4); Cat = 3,5-di-tert-butyl-catecholate (3,5-DBCat), linker = Bipy (5); DABCO (9); Cat = 4,5-(piperazine-1,4-diyl)-3,6-di-tert-butylcatecholate (pip-3,6-DBCat), linker = Bipy (6); DABCO (10); Cat = 4,5-dichloro-3,6-di-tert-butylcatecholate (4,5-Cl₂-3,6-DBCat), linker = Bipy (7); DABCO (11); and Cat = 4,5-dimethoxy-3,6-di-tert-butylcatecholate (4,5-(MeO)₂-3,6-DBCat), linker = Bipy (8). The same reaction of (4,5-Cl₂-3,6-DBCat)SbPh₃ with DABCO in an open atmosphere results in a formation of 1D coordination polymer {[(4,5-Cl₂-3,6-DBCat)SbPh₃·H₂O]·DABCO}_n (12). Bis-catecholate complex Ph₃Sb(Cat-Spiro-Cat)SbPh₃ reacts with Bipy as 1:1 yielding a rare macrocyclic tetranuclear compound {Ph₃Sb(Cat-Spiro-Cat)SbPh₃∙(Bipy)}₂ (13). The molecular structures of 1, 3, 4, 5, 8, 10, 12, and 13 in crystal state were established by single-crystal X-ray analysis. Complexes demonstrate different types of relative spatial positions of mononuclear moieties. The nature of chemical bonds, charges distribution, and the energy of Sb...N interaction were investigated in the example of complex 5. The electrochemical behavior of the complexes depends on the coordinated N-donor ligand. The coordination of pyrazine, Bipy, and PySSPy at the antimony atom changes their mechanism of electrooxidation: instead of two successive redox stages Cat/SQ and SQ/Cat, one multielectron stage was observed. The coordination of the DABCO ligand is accompanied by a significant shift in the oxidation potentials of the catecholate ligand to the cathodic region (by 0.4 V), compared to the initial complex.