Dc. Bebout et al., Comparison of heteronuclear coupling constants for isostructural nitrogen coordination compounds of Cd-111/113 and Hg-199, INORG CHEM, 38(6), 1999, pp. 1126-1133
The complexation of Cd(II) by the tripodal ligand tris[(2-pyridyl)methyl]am
ine and dipodal ligand bis[(2-pyridyl)methyl]amine was investigated by solu
tion-state NMR and X-ray crystallography. Cadmium coordination compounds ex
hibiting rarely observed solution-state NMR H-1-Cd-111/113 satellites were
characterized. The eight-coordinate complex [Cd(TMPA)(2)](ClO4)(2). toluene
(1) crystallizes in the triclinic space group P1 with a = 9.629(2) Angstro
m, b = 11.020(2) Angstrom, c = 11.641(2) Angstrom, alpha = 114.069(13)degre
es, beta = 97.492(13)degrees, gamma = 91.034(14)degrees, and Z = 1. The ave
rage Cd-N-amine distance is 2.53(4) Angstrom and the average Cd-N-pyridyl d
istance is 2.54(6) Angstrom. The complex [Cd(BMPA)(NCCH3)(OH2)(OClO3)][Cd(B
MPA)(2)](ClO4)(3).(CH3CN) (2) crystallizes in the triclinic space group P (
1) over bar with a = 10.446(2) Angstrom, b = 16.653(3) Angstrom, c = 17.736
(3) Angstrom, alpha = 62.479(9)degrees, beta = 80.606(14)degrees, gamma = 8
4.66(2)degrees, and Z = 2. In the pseudo-octahedral monocation, the nitroge
n-containing ligands occupy equatorial positions with Cd-N distances of 2.3
21(8), 2.283(7), and 2.263(8) Angstrom for the amine, pyridyl (average) and
acetonitrile nitrogens, respectively. Significant axial interactions occur
with Cd-O bond distances of 2.313(7) Angstrom (water) and 2.478(7) Angstro
m (perchlorate). In the pseudo-trigonal prismatic dication, the average Cd-
N-amine distances is 2.395(5) Angstrom and the average Cd-N-pyridyl distanc
e is 2.362(8) Angstrom. The solid-state structures and solution-state NMR t
rends were very similar to recently reported isovalent complexes of Hg(II),
providing an exceptional opportunity tb compare coupling constants of coor
dination compounds. Implications for the use of Cd-111/113 and Hg-199 NMR a
s metallobioprobes are discussed.