Synthesis of Binuclear Palladium(I) and (II) Complexes Containing (Benzylthiomethyl)diphenylphosphine as Bridging Ligand. The X-Ray Crystal Structure and Reactions of [Pd2Cl2(μ-PhCH2SCH2PPh2)2]

• Published in: Bulletin of the Chemical Society of Japan Vol. 63; no. 7; pp. 1961 - 1967
• Main Authors: Fuchita, Yoshio, Hardcastle, Kenneth I, Hiraki, Katsuma, Kawatani, Masanori
• Format: Journal Article
• Language: English
• Published: The Chemical Society of Japan 01.07.1990
• ISSN: 0009-2673; 1348-0634
• DOI: 10.1246/bcsj.63.1961

The side-by-side type palladium(I) complex [Pd2Cl2(μ-btmp)2] (2) was synthesized either by the reaction among [PdCl2(NCMe)2], [Pd(dba)2] (dba=dibenzylideneacetone), and (benzylthiomethyl)diphenylphosphine (btmp) or by the reaction of [PdCl2(btmp-P)2] (1) and [Pd(dba)2]. The structure of 2 was established by a single-crystal X-ray diffraction study; the crystals were monoclinic, space group P21/c, with a=13.537(3), b=19.550(3), c=17.240(4) Å, β=114.59(2)°, and Z=4; final R factor 0.049 for 5490 observed reflections. The structure showed that there is a metal-metal bond [Pd–Pd 2.590(2) Å]. Treatment of 2 with sodium iodide afforded the diiodo complex [Pd2I2(μ-btmp)2], whereas that with 4-methylpyridine (4-MePy) in the presence of AgClO4 gave [Pd2(μ-btmp)2(4-MePy)2][ClO4]2. Moreover, 2 reacted with substituted acetylenes (RC≡CR′: R=Ph, R′=H; R=CO2Me, R′=H; R=R′=CO2Me) to yield A-frame type complexes [Pd2Cl2(μ-RC=CR′)(μ-btmp)2]. All the complexes obtained in this study were characterized by means of elemental analysis, and IR and NMR spectroscopy.