Ni-Fe and Pd-Fe Interactions in Nickel(II) and Palladium(II) Complexes of a Ferrocene-Bridged Bis(imidazolin-2-imine) Ligand.

ABSTRACT

The bis(imidazolin-2-imine) ligand N,N'-bis(1,3-diisopropyl-4,5-dimethylimidazolin-2-ylidene)-1,1'-ferrocenediamine, fc(NIm)2 (1) was prepared. Its reaction with [NiCl2(dme)] (dme = 1,2-dimethoxyethane) or [PdCl2(MeCN)2] afforded the tetrahedral, paramagnetic complex [(1-κ(2)N,N')NiCl2] (6a) or the diamagnetic, square-planar complex [(1-κ(2)N,N')PdCl2] (6b), respectively. For the latter, slow rearrangement to the ionic complex [(1-κFe,κ(2)N,N')PdCl]Cl, [7]Cl, was observed, which was followed by (1)H NMR and UV/vis spectroscopy. Treatment of [7]Cl with NaBF4 afforded [7]BF4; the palladium atoms in both cations adopt square-planar environments with short Fe-Pd bonds (ca. 2.65 Å). In addition, a series of dicationic complexes of the type [(1-κFe,κ(2)N,N')ML](BF4)2 (8a M = Ni, L = MeCN; 8b M = Pd, L = MeCN; 9a M = Ni, L = PMe3; 9b M = Pd, L = PMe3) was prepared from 6a (M = Ni) or [7]BF4 by chloride abstraction with NaBF4 or AgBF4 in the presence of acetonitrile or trimethylphosphine, respectively. In the presence of triphenylphosphine, the palladium(II) complex [(1-κFe,κ(2)N,N')Pd(PPh3)](BF4)2 (10) was isolated. Iron-nickel and iron-palladium bonding in these complexes was studied experimentally by NMR, UV/vis, and Mössbauer spectroscopy and by cyclic voltammetry. Detailed DFT calculations were carried out for the cations [(1-κFe,κ(2)N,N')M(MeCN)](2+) in the 8a/8b couple, with Bader's atoms in molecules theory revealing the presence of noncovalent, closed-shell metal-metal interactions. Potential energy surface scans with successive elongation of the Fe-M bonds allow an estimation of the iron-metal bond dissociation energies (BDE) as BDE(Fe-Ni) = 11.3 kcal mol(-1) and BDE(Fe-Pd) = 24.3 kcal mol(-1).