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The reactivity of tin(II) catecholate complex CatSn (1) (where Cat = 3,6‐di‐tert‐butylcatecholate dianion) and two o‐amidophenolate complexes DippAPSn (2) and PhAPSn (3) [where DippAP = 4,6‐di‐tert‐butyl‐N‐(2,6‐diisopropylphenyl)amidophenolate; PhAP = 4,6‐di‐tert‐butyl‐N‐(phenyl)amidophenolate dianions] towards different reagents is reported. Products of the insertion of 1 and 2 into the S–S bond of tetramethylthiuram disulfide were obtained and characterised by X‐ray diffraction analyses. The low temperature oxidation of complexes 1 and 2 with 2‐ethoxy‐3,6‐di‐tert‐butylphenoxy radical enabled us to detect formation of paramagnetic tin(II) derivatives containing the radical‐anion form of the redox‐active ligand. The reaction of tin derivative 3 with Ni(CO)4 leads to substitution of one of the CO groups in the latter with the formation of a new bimetallic product.

The interaction of 3,6-di-tert-butyl-o-benzoquinone (3,6-Q) with indium in toluene leads to the tris-o-semiquinolate derivative (3,6-SQ)(3)In (3,6-SQ - radical-anion of 3,6-Q). According to single-crystal X-ray diffraction analysis, this complex has a trigonal prismatic structure. Magnetic measurements revealed that the exchange interactions between odd electrons of the paramagnetic ligands in (3,6-SQ)(3)In are antiferromagnetic in character. The treatment of (3,6-SQ)(3)In with 2,2'-dipyridyl (Dipy) causes the displacement of one o-quinone ligand and the formation of the (3,6-SQ)In(Dipy)(3,6-Cat) (3,6-Cat - dianion of 3,6-Q) derivative containing mixed charged o-quinoid ligands. The reaction of InI with (3,6-SQ)K in THF solution is accompanied by a redox process and the potassium-indium(iii) catecholate derivative was obtained as a result. The oxidation of InI with 3,6-Q in THF produces the dimeric In(iii) iodo-catecholate complex [(3,6-Cat)(2)In·2THF]InI(2). The same derivative can be synthesized by the interaction of indium metal with a mixture of I(2) and 3,6-Q.

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New tris‐o‐benzosemiquinonato complexes of Al, Ga, and In based on the sterically hindered o‐benzoquinone 5,8‐di‐tert‐butyl‐2,3‐dihydro‐1,4‐ethanoquinoxaline‐6,7‐dione (NN‐3,6‐Q) were synthesized. The structures of the hexacoordinate metal compounds were investigated by X‐ray diffraction. The magnetic properties of the complexes obtained were found to be strongly dependent on their molecular geometry. The octahedral Al and Ga derivatives demonstrate ferromagnetic exchange between the magnetic centers, whereas the trigonal‐prismatic In complex shows an antiferromagnetic coupling.