Abstract
Ferrocene P,N-ligands have been extensively studied due to their favorable catalytic properties. This contribution focuses on a pair of new, isomeric ferrocene phosphinoamines, FcNHCH2CH2PPh2 (1) and FcN(Me)CH2PPh2 (2), which were prepared from aminoferrocene, converted to the respective phosphine selenides (1-Se and 2-Se) and further studied as ligands in Pd(II) complexes containing the 2-(dimethylamino-κN)phenyl-κC1 auxiliary (LNC) ligand. Thus, cleavage of the dimeric precursor [(LNC)Pd(μ-Cl)]2 with the phosphinoamines afforded the corresponding phosphine complexes [(LNC)PdCl(1-κP)] (5) and [(LNC)PdCl(2-κP)] (6) with trans-P,N configuration. The subsequent removal of the chloride ligand with AgClO4 from 5 produced the cationic bis-chelate complex [(LNC)PdCl(1-κ2P,N)]ClO4 (7), whereas an analogous reaction with 6 gave no defined product. The phosphinoamines and their complexes were characterized by elemental analysis and common spectroscopic methods, and the crystal structures of 1, 2, and 7 were determined by single-crystal X-ray diffraction analysis. A cyclic voltammetry study, supported by DFT calculations, revealed that the primary electrochemical oxidation of these compounds occurs at the ferrocene unit.
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