Diastereomerically Pure Heterodi- and Heterotetrametallic (Pd and Pt) Compounds: A Study of the Effect Induced by the Binding Mode of a Ferrocene-Containing Ligand on Their Electrochemical Properties

作者：Talancon Daniel; Lopez Concepcion^*; Font Bardia Merce; Calvet Teresa; Roubeau Olivier

来源：European Journal of Inorganic Chemistry, 2014, 2014(1): 213-220.

DOI：10.1002/ejic.201301274

• Electrochemistry
• Chirality
• Coordination modes
• Sandwich complexes
• Cyclometallated compounds

The reaction of (1S,2R)-[(eta(5)-C5H5)Fe{(eta(5)-C5H4)-CH=N-CH(Me)-CH(OH)(C6H5)}] (1) with Na-2[PdCl4] in the presence of Na(OAc)center dot 3H(2)O produced three diastereomerically pure tetrametallic cyclopalladated complexes (6b(I)-6b(III)). In two of them (6b(I) and 6b(II)), the imine 1 adopts the [C(sp(2),ferrocene),N](-) mode of binding, but they differ in the planar chirality of the 1,2-ferrocenyl unit (S-p in 6b(I) and R-p in 6b(II)), whereas ligand 1 in 6b(III) acts as a [C(sp(2),phenyl),N](-) group. Treatment of 6b(I)-6b(III) with PPh3 gave [Pd{kappa(2)-C,N{(eta(5)-C5H3)-CH=N-CH(Me)-CH(OH)(C6H5)}Fe(eta(5)-C5H5)}Cl(PPh3)] (7b(I), 7b(II)) and [Pd{kappa(2)-C,N{(C6H4)-CH(OH)-CH(Me)-N=CH-(eta(5)-C5H4)}Fe(eta(5)-C5H5)}Cl(PPh3)] (7b(III)). The Pt-II compounds [Pt{kappa(2)-C,N{(eta(5)-C5H3)-CH=NCH(Me)CH(OH)(C6H5)}Fe(eta(5)-C5H5)}Cl(PPh3)] [(S-p,1S,2R) and (R-p,1S,2R) diastereomers, 7a(I) and 7a(II), respectively)] have also been prepared. The results of electrochemical studies of 6b(I)-6b(III), 7b(I)-7b(III), 7a(I), 7a(II) and related Pt-II complexes with 1 acting as an (N) or (N,O)(-) ligand are also reported. Comparison of the results provides conclusive evidence for the relative influence of the mode of binding of the ligand, the nature of the M-II atom, the type of metallated atom C(sp(2),phenyl or ferrocenyl), the ancillary ligands and their relative disposition on the electrochemical properties of this type of compound.

• 出版日期2014-1