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The synthesis and characterization of divalent palladium and platinum complexes of the type PdX2(Ar-BIAN) (X = Cl, Br, I, OC(O)Me), PdCl2(Ph-BIC) and PtCl2(Ar-BIAN) is described. These complexes contain the rigid bidentate nitrogen ligands bis(arylimino)acenaphthene (Ar-BIAN; Ar = Ph, p-MeC6H4, p-MeOC6H4, o,o‘-Me2C6H3, o,o‘-i-Pr2C6H3) or bis(phenylimino)camphane (Ph-BIC), which act as σ-donor ligands to the metal center, as was deduced from the observed shifts in the IR and NMR spectra of the complexes. Electrochemical reduction of PdCl2(Ar-BIAN) complexes in THF or DMF occurs via two one-electron reductions and affords the complex PdICl(Ar-BIAN)•-, which slowly produces some Pd0(Ar-BIAN) complex. PdICl(Ar-BIAN)•- reacts with iodomethane, whereas with iodobenzene or bromobenzene no reaction was observed. PdICl(Ar-BIAN)•- reacts with free Ar-BIAN or the alkenes dimethyl fumarate, dimethyl maleate, and methyl acrylate, giving complexes of the formulas PdICl(Ar-BIAN)2•- and PdICl(Ar-BIAN)(alkene)•-, respecti...

Divalent Palladium and Platinum Complexes Containing Rigid Bidentate Nitrogen Ligands and Electrochemistry of the Palladium Complexes1

Divalent Palladium and Platinum Complexes Containing Rigid Bidentate Nitrogen Ligands and Electrochemistry of the Palladium Complexes¹