Abstract
The synthesis of symmetric and non-symmetric 5,5'-linked disalophen Ni(ii) complexes by the Suzuki-Miyaura-reaction is reported. Also, the synthesis and structural characterization of four Ni(ii)-precursor complexes are presented. The 5-Br-substituted mononuclear complexes and are coupled to the pinacolborane substituted complexes and yielding the four dinuclear dinickel complexes in good yields. The crystal structure of dinuclear complex was obtained revealing a coplanar arrangement between the two salophen fragments. Electronic spectra as well as DFT-calculations on the ground states and excitation energies are reported and they reveal a small coupling between the electronically saturated Ni-salophen complexes.
Highlights
In this paper we present a method for the synthesis of symmetric and unsymmetric 5,5′-bonded dinuclear nickel-salophen-complexes by cross-coupling of mononuclear precursorcomplex building blocks
The absence of bivalent highly Lewisacidic metal ions during synthesis that could exchange with the coordinated nickel(II) ion is an advantage over other C–C cross-coupling reactions
The synthesis of the precursors was carried out following the procedure of Kleij et al except for the choice of solvents.[3]
Summary
Oligonuclear salen-complexes gained a lot of attention recently, owing to their unique combination of an easy-tomodify non-innocent ligand with a very broad range of central metal-ions, ranging from alkali- over 3d metal- to lanthanideions.[1,2] Due to this versatility this class of compounds has been investigated for a variety of applications and properties, including metal–organic frameworks,[3,4] catalysis,[5,6] and redox behavior.[7,8,9] the unique properties of salencomplexes have led to their established role in the research on molecule-based magnetism.[10,11,12,13] In a recent study, 5,5′dibromo-salophen-cobalt(II)-molecules have been oligomerized on a gold-surface in an Ullmann-type coupling reaction under the formation of 5,5′-C–C-coupled oligomeric complex chains.[14] These molecular chains exhibited a unique magnetic behavior, which is caused by the interaction of the magnetic orbitals of the cobalt atoms with the extended π-system of the ligand along the chain.[15] Based on this result, an on-surface hetero-coupling strategy was developed to combine different
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