Abstract
1′-(Diphenylphosphino)ferrocenecarboxylic acid (Hdpf) reacts with nickel(II) halides and nickel(II) thiocyanate to give the paramagnetic complexes [NiX2(Hdpf-κP)2] (X = Cl, 1; Br, 2; I, 3) and the diamagnetic planar isothiocyanato complex [Ni(SCN-κN)2(Hdpf-κP)2] (4), respectively. In situ neutralization of Hdpf followed by reaction with nickel(II) sulfate affords the salt [Ni(dpf)2] (5). The halide complexes 1–3 easily undergo dissociative decomposition in polar donor solvents; compound 5 is insoluble in all common solvents. All compounds were characterized by IR and UV/vis spectroscopies and magnetic measurements in the solid state. The solid-state structure of the solvate 4·2CHCl3 was determined by single-crystal X-ray diffraction. A series of complexes, including the ligand Hdpf and its Ca salt (6) as reference compounds, were further studied by X-ray photoelectron spectroscopy. Spectral data and magnetic measurements indicate compound 5 contains the dpf − anion as a P,O-coordinated ligand.
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