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

• Published in: Inorganic chemistry 2015-12, Vol.54 (24), p.12032-12045
• Main Authors: Jess, Kristof, Baabe, Dirk, Bannenberg, Thomas, Brandhorst, Kai, Freytag, Matthias, Jones, Peter G, Tamm, Matthias
• Format: Article
• Language: English
• ISSN: 0020-1669; 1520-510X
• DOI: 10.1021/acs.inorgchem.5b02457

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-κ2 N,N′)­NiCl2] (6a) or the diamagnetic, square-planar complex [(1-κ2 N,N′)­PdCl2] (6b), respectively. For the latter, slow rearrangement to the ionic complex [(1-κFe,κ2 N,N′)­PdCl]­Cl, [7]­Cl, was observed, which was followed by 1H 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,κ2 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,κ2 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,κ2 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.