Redox-controlled, reversible rearrangement of a tris(2-pyridylthio)methyl ligand on nickel to an isomer with an “N,S-confused” 2-pyridylthiolate arm.

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).

Synthesis and characterization of tris(2-pyridylthio)methanido Zn complex with a Zn-C bond and DFT calculation of its one-electron oxidized species.

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)).

Thiacalix[3]pyridine produces a stable mononuclear rhodium(II) complex with mutual Jahn-Teller effect.

Thiacalix[3]pyridine (Py3S3) consists of pyridines and bridging sulfur atoms producing a stable octahedral mononuclear Rh(II) complex [Rh(II)(Py3S3)2]2+ showing mutual Jahn-Teller effect, a metal based reversible redox couple of Rh(III/II) at 0.02 V vs. SCE and a g(perpendicular) > g(||) relationship in EPR measurements.

A complete series of copper(II) halide complexes (X = F, Cl, Br, I) with a novel Cu(II)-C(sp3) bond.

A complete series of copper(ii) halide complexes [CuX(tptm)](X = F (), Cl (), Br (), I (); tptm = tris(2-pyridylthio)methyl) with a novel Cu(II)-C(sp(3)) bond has been prepared by the reactions of [Cu(tptm)(CH(3)CN)]PF(6)(.PF(6)) with corresponding halide sources of KF or n-Bu(4)NX (X = Cl, Br, I), and the trigonal bipyramidal structures have been confirmed by X-ray crystallography and/or EPR spectroscopy. The iodide complex easily liberates the iodide anion in acetonitrile forming the acetonitrile complex as a result.