title: Redox-controlled, reversible rearrangement of a tris(2-pyridylthio)methyl ligand on nickel to an isomer with an “N,S-confused” 2-pyridylthiolate arm.
abstract: 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.
authors: Department of Material Science, Osaka City University, Sumiyoshi-ku, Osaka, Japan.
authors: Naoto
authors: N
authors: Kuwamura
authors: Ken'ichi
authors: K
authors: Kitano
authors: Masakazu
authors: M
authors: Hirotsu
authors: Takanori
authors: T
authors: Nishioka
authors: Yoshio
authors: Y
authors: Teki
authors: Ryoko
authors: R
authors: Santo
authors: Akio
authors: A
authors: Ichimura
authors: Hideki
authors: H
authors: Hashimoto
authors: L James
authors: LJ
authors: Wright
authors: Isamu
authors: I
authors: Kinoshita