Mercury(II) complexes containing new ortho-functionalized asymmetric triazene ligands: synthesis, crystal structures, and solution studies
Synthesis of two new asymmetric ligands: 1-(2-ethoxyphenyl)-3-(2-methoxycarbonylphenyl)triazene (HL) (1) and 1-(2-methoxyphenyl)-3-(2-methoxycarbonylphenyl)triazene (HL′) (2) are reported. The prepared triazenes are functionalized by ethoxy and methoxy groups in the ortho positions, respectively. The related monomeric complexes, [HgL 2] (3) and [HgL′ 2] (4), were prepared by the reacting of the corresponding ligands with Hg(NO3)2 salt in methanol as solvent. All compounds were characterized by CHN analysis, FT-IR, 1H NMR, and 13C NMR spectroscopy. According to the crystal structures of 1 and 2, the N–N bond distances indicate the presence of alternating single and double bonds, and hence the –N=N–NH– moiety. On coordination, each triazene was deprotonated and as a result, a resonance structure is formed between nitrogens which let them to be a tridentate ligand. In the crystal structure of 3, [HgL 2], the central Hg(II) is surrounded by two N atoms from interlocked L forming linear geometry, in which the other four Hg–N and Hg–O bonds are longer and can only be regarded as weak secondary bonds. An interesting feature of 3 is also the presence of π…π [centroid–centroid distance of 3.744(3) Å] and C–H…π interactions. The results of solution studies for the formation of 3 in methanol support its solid-state stoichiometry.
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