Abstract
Palladium(II) complexes of cis- and trans-1,2-bis(dimethylarsino)ethylene, 1 and 2, respectively, in the metal: ligand ratios 1:1 and 1:2 are described. Their structures are discussed in terms of nuclear magnetic resonance, infrared, conductivity, and analytical data, and by comparison with the corresponding platinum(II) complexes (1). The cis-isomer, cis-ED, is a strong chelating ligand and forms the complexes Pd(cis-ED)X2, 9 (X = Cl−, Br−), and Pd(cis-ED)2X2•3H2O, 8 (X = Cl−, Br−, ClO4−, PF6−). The trans-isomer, trans-ED is a bridging ligand and forms the dimeric complexes, [Pd(trans-ED)X2]2, 10 (X = Cl−, Br−), and Pd2(trans-ED)4X4•3H2O, 7 (X = Cl−, Br−, ClO4−, PF6−). All these complexes contain 4-coordinate, square planar palladium(II). The anhydrous form of 7 (X = Cl−) shows evidence for a Pd—Cl bond, suggesting 5-coordination in the solid state. Room temperature irradiation (with ultraviolet light) of 7 (X = Cl−), in non-aqueous solvents, causes isomerization of the ligand and the formation of complex 8 (X = Cl−). No change occurs under these conditions in aqueous solutions. Contrary to the original suggestion for the corresponding platinum(II) derivative, 10 (M = Pt(II), ref. 1) far infrared evidence supports a cis-configuration about the metal ion rather than the trans-configuration, 6.
Published Version
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