Palladium(II) compounds containing sigma[Pd-C-sp2(ferrocene)] bonds and ferrocenyloximes as bidentate {CN}- ligands - X-ray crystal structure of [Pd{[(eta(5)-C5H3)-C(CH3)=N(OH)]Fe(eta(5)-C5H5)}Cl(PPh3)]

Ferrocenyloximes of general formula [{(eta(5)-C5H4)-C(R)=N(OH)}Fe(eta(5)-C5H5)}] with R=H (1a) or CH3 (1b) react at room temperature in methanol with Na-2[PdCl4] and Na(CH3COO). 3H(2)O in a 1:1:1 molar ratio producing the di-mu-chloro-bridged derivatives [Pd{[(eta(5)-C5H3)-C(R)=N(OH)]Fe(eta(5)-C5H5)}(mu-Cl)](2) (with R=H(2a) or CH3 (2b)) which undergo cleavage of the 'Pd(mu-Cl)(2)Pd' units in the presence of PPh3 to give the mononuclear cyclopalladated complexes [Pd{[(eta(5)-C5H3)-C(R)=N(OH)]Fe(eta(5)-C5H5)}Cl(PPh3)] (with R=H (3a) or CH3 (3b)). The molecular structure of compound 3b has been determined by X-ray crystallography: monoclinic, space group C2/c with a=27.485(5) Angstrom; b=9.954(2) Angstrom; c=24.778(4) Angstrom and beta=131.07(3)degrees. These studies confirm the presence of a five-membered palladacycle fused with the C5H3 ring of the ferrocenyl moiety, and a trans arrangement of the phosphine and the nitrogen. (C) 1997 Elsevier Science S.A.