Tin(II) Complexes Based on N-Alkyl-Substituted o-Amidophenolate Ligands: Acid–Base and Redox Transformations

Resumo

New stannylene ^AdAPSn (I) based on 4,6-di-tert-butyl-N-adamantyl-o-aminophenol is synthesized and structurally characterized. Stannylene I in the crystalline state forms infinite chains due to intermolecular donor–acceptor Sn–N and metallophilic Sn···Sn interactions. The reactivities of compound I and earlier synthesized ^t-BuAPSn (II) are studied using their redox and acid–base reactions. Stannylenes I and II are inserted at the S–S bond of tetramethylthiuram disulfide to form the corresponding tin(IV) dithiocarbamate complexes. The reactions with soft one-electron oxidants involve the redox-active o-amidophenolate ligand and generate labile paramagnetic stannylenes studied by EPR spectroscopy. The presence of a lone electron pair at the low-valence tin atom is a reason for its basic properties, which is demonstrated for the reaction of compound I with nanocarbonyl iron. The structures of selected synthesized compounds are determined by X-ray diffraction analysis (СIF files CCDC nos. 1905419–1905421).