Characterization of HgCl2 Tridentate Amine Complexes by X-ray Crystallography, NMR and ESI-MS
Publication Date
2-2013
Description
Two new HgCl2 complexes of tridentate nitrogen ligands were characterized by X-ray crystallography, proton NMR spectroscopy and ESI-MS. The five-coordinate complex [Hg(BMPA)Cl-2] (1) (BMPA = bis(2-pyridylmethyl)amine) crystallized from acetonitrile/m-xylene by slow evaporation in the monoclinic space group P2(1)/n with a = 8.3896(8) , b = 12.8020(13) , c = 13.3526(13) , alpha = 90A degrees, beta A = 90.480(2)A degrees, gamma A = 90A degrees and z = 4. The square pyramidal structure (tau = 0.009) has approximate C (s) symmetry. Despite comparable Hg-N bond lengths in 1, inversion of the central nitrogen was rapid on the chemical shift time scale in dilute solution except at very low temperatures. The related complex [Hg(BEPA)Cl-2] (2) (BEPA = bis(2-{pyrid-2-yl}ethyl)amine) crystallized from acetonitrile/ethyl acetate/hexanes by slow diffusion in the orthorhombic space group Pnma with a = 13.424(3) , b = 14.854(3) , c = 8.118(2) , alpha = 90A degrees, beta A = 90A degrees, gamma A = 90A degrees and z = 4. The mixed geometry structure (tau = 0.56) also has crystallographic mirror symmetry as well as C (s) point group symmetry. In dilute acetonitrile solution, 1 was stable while 2 slowly converted to a more thermodynamically stable complex.
Journal
Journal of Chemical Crystallography
Volume
43
Issue
2
First Page
108
Last Page
115
Department
Chemistry
Link to Published Version
Recommended Citation
Bebout, Deborah C.; Bowers, Edith V.; Freer, Rachel E.; Kastner, Margaret E.; Parrish, Damon A.; and Butcher, Raymond J.. "Characterization of HgCl2 Tridentate Amine Complexes by X-ray Crystallography, NMR and ESI-MS." Journal of Chemical Crystallography (2013) : 108-115.