K. Yamasaki, Hiroaki Saito, M. Tadokoro
Sep 1, 1997
Citations
0
Influential Citations
5
Citations
Journal
Bulletin of the Chemical Society of Japan
Abstract
2,6-Bis(chloromethyl)pyridine was oxidatively added to [IrCl(PPh3)3] to give cis(P,P)-[IrCl2(ClCH2-py-CH2-C,N)(PPh3)2] (ClCH2-py-CH2 = {2-(6-chloromethyl)pyridyl}methyl) (1a), of which the cycloiridated structure has been established by an X-ray analysis. Complex 1a further reacts with [RhCl(PPh3)3] to afford an Ir(III)–Rh(III) complex [IrRhCl2(μ-Cl)2(μ-CH2-py-CH2-C,N,C′)(PPh3)3](CH2-py-CH2 = 2,6-dimethylpyridine-α,α′-diyl) (3). Upon prolonged heating in toluene, 3 liberates one triphenylphosphine ligand and [IrRhCl2(μ-Cl)2(μ-CH2-py-CH2-C,N,C′)(PPh3)2] (4) is formed. X-Ray crystal structure determinations of 3 and 4 have revealed their dinuclear structures, in which the metals are connected by two Cl atoms and a CH2-py-CH2 group acting, in 3, as a κC (for Ir) : κC,κN (for Rh)-bridging ligand, while, in 4, as a κC (for Rh) : κC,κN (for Ir)-bridging ligand. The structure of the corresponding Rh(III)–Rh(III) complex, [Rh2Cl4(μ-CH2-py-CH2)(PPh3)2] (6), which was incorrectly assigned based on its NMR spectral ...