Synthesis and Coordination Chemistry of Doubly-Tridentate Tripodal Pyridazine and Pyrimidine-Derived Ligands: Structural Interplay Between M2L and M2L2 (M = Ni and Pd) Complexes and Magnetic Properties of Iron(II) Complexes

Abstract

The coordination chemistry of three bridging doubly-tridentate ligands, including the known compound 3,6-bis(di-2-pyridylmethyl)pyridazine (1), which is structurally similar to 1,4-bis(di-2-pyridylmethyl)phthalazine (2), and two pyrimidine-linked compounds 4,6-bis(di-2-pyridylmethyl)pyrimidine (3), and 4,6-bis(di-2-pyridylamino)pyrimidine (4), was investigated with FeII, NiII, and PdII metal salts. Ligands 3 and 4 were synthesized in one-pot reactions from easily obtained starting materials; compound 3 was synthesized from di-2-pyridylmethane and 4,6-diiodopyrimidine in 48% yield, while ligand 4 was prepared by reacting di-2-pyridylamine with 4,6-dichloropyrimidine in 27% yield. During the synthesis of 4, an additional compound, 4-chloro-6-(di-2-pyridylamino)pyrimidine (5), with only one tridentate binding site was obtained in 30% yield. Reactions of 1, 3, and 4 with FeII or NiII salts gave two types of complexes, either discrete M2L or M2L2 assemblies. The PdII complexes obtained were also characterized as discrete M2L complexes. The compounds were characterized by a combination of NMR and IR spectroscopy, microanalysis and X-ray crystallography. Noticeable differences in the structures obtained for NiII coordination complexes with the carbon-linked (3) and nitrogen-linked (4) ligands were observed, whereby the nitrogen linker adopted a trigonal planar geometry and prevented tridentate facial coordination of the octahedral metal centres. The magnetic properties of dinuclear FeII complexes of 1 were examined to see if they showed spin-crossover effects, a feature recently observed by others in other dinuclear helicate complexes, but the complexes remained high-spin at all temperatures between 300 and 2 K.