Investigation of the mercury(II) coordination chemistry of tris[(1-methylimidazol-2-yl)methyl]amine by X-ray crystallography and NMR

The coordination chemistry of Hg(II) with tris[(1-methylimidazol-2-yl)methyl]amine (TMIMA) was investigated. The structures of [Hg (TMIMA)2](ClO4)2(1), [Hg(TMIMA)(NCCH3)](ClO4)2(2) and [Hg(TMIMA)Cl]2(HgCl4)(3) were characterized by X-ray crystallography. Complex 1 has six strong Hg-Nimidazoyl bonds ranging from 2.257(5) to 2.631(6) (angstrom). Ligand geometry suggests the Hg-N(NR3) distances of 2.959(6) (angstrom) in 1 reflects weak bonding interactions. This complex has a 199Hg chemical shift of -1496 ppm, significantly upfield from nitrogen coordination complexes with lower coordination numbers. The five-coordinate complex 2 has Hg-N (NR3), Hg-Nimidazoyl and Hg-Nacetonitrile bond lengths of 2.642(8), 2.198(5) and 2.264(11) (angstrom) , respectively. Complex 3 is also five coordinate, with Hg-N(NR3), Hg-Cl and average Hg-Nimidazoyl distances in the cations of 2.758(7), 2.424(2) and 2.29(4) (angstrom), respectively. Conditions for slow exchange on the J(HgH) coupling time-scale were found for both 1 1 metal-to-ligand complexes in acetonitrile-d3. Observed heteronuclear coupling constants were similar to those associated with Hg(II) substituted proteins with histidine-metal bonds. Solution and solid-state comparisons to the Hg(II) coordination chemistry of tetradenate pyridyl ligands are made. Relevance to development of 199Hg NMR as a metallobioprobe is discussed.