A one-dimensional copper(ii) complex with pyridine-2-sulfonate donors, [{Cu(3-mpSO 3 ) 2 } n ] (3-mpSO 3 = 3-methylpyridine-2-sulfonate), is formed via the air oxidation of 3-mpds (2,2A-bis(3-methylpyridyl)disulfide) in the presence of CuBr 2 , and a mononuclear zinc complex, [Zn(3-mpSO 3 ) 2 (H 2 O) 2 ], which has two-dimensional H-bonded networks and luminescent properties in solid state, is prepared by the reaction of ZnBr 2 with 3-mpSO 3 H.

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Tris(2-pyridylthio)methane (tptmH) reacts with ZnCl(2) producing the Zn-C containing complex of [ZnCl(tptm)], whose cyclic voltammogram shows an irreversible oxidation peak at 0.2 V vs. E(0')(Fc(+/0)). DFT calculations suggested that 1e(-) oxidation should occur at the tptm ligand resulting in the cleavage of the Zn-C bond, leading to decomposition of the complex.

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Interchange between the nickel +2 and +3 oxidation states precisely controls the reversible rearrangement of the tris(2-pyridylthio)methanide (tptm) ligand in the organometallic nickel(II) complex [{Ni(μ-Br)-(tptm)}(2)] (2). Oxidation of 2 first gives the corresponding Ni(III) complex [{Ni(μ-Br)(tptm)}(2)][PF(6)](2) (4). However, in solution the tptm ligand in 4 slowly undergoes a rearrangement, in which the N and S atoms of one of the pyridylthiolate arms exchange Ni and C bonding partners, thereby resulting in an "N,S-confused" isomer of tptm in the product, [NiBr(bpttpm)]PF(6) (5; bpttpm= bis(2-pyridylthio)(2-thiopyridinium)-methyl). Reduction of 5 reverses this ligand rearrangement and 2 is reformed quantitatively. The individual steps involved in these unusual ligand rearrangements were investigated by a number of methods, including voltammetric analysis, and a mechanism for this process is proposed. X-ray crystal structure determinations of the key compounds 2, 4 and 5 have been obtained.