title: Weak Interactions in Ternary Copper(II) Complexes with Iodotyrosinates. Biological Significance of the Iodines in Thyroid Hormones.
abstract: Structures and spectroscopic studies have been carried out on ternary copper(II) complexes, Cu(DA)(AA), with aromatic amino acids (AA = 3,5-diiodo-L-tyrosinate (L-I(2)tyr), 3-iodo-L-tyrosinate (L-Ityr), L-tyrosinate) and diamines (DA = 1,10-phenanthroline, 2,2'-bipyridine (bpy), 2-(aminomethyl)pyridine, histamine (hista), or ethylenediamine). The charge transfer (CT) absorption bands observed in the near UV region and the CD spectral magnitude anomaly observed in the d-d region indicated an effective aromatic ring stacking interaction between the side-chain phenol ring of AA and the aromatic diamine DA in the complexes in solution. Two complexes, [Cu(bpy)(L-Ityr)(H(2)O)].NO(3).CH(3)OH.H(2)O (1) and [Cu(hista)(L-I(2)tyrO(-))(H(2)O)](2).2H(2)O (2), where O(-) represents the deprotonated form of the phenol hydroxyl group, were isolated as single crystals, and their structures were determined by X-ray analysis. Both 1 and 2 crystallized in the monoclinic space group P2(1), with a = 7.549(1) Å, b = 11.431(1) Å, c = 14.292(2) Å, beta = 100.08(1) degrees, and Z = 2 for 1 and a = 9.9642(9) Å, b = 15.825(1) Å, c = 12.451(1) Å, beta = 91.565(7) degrees, and Z = 2 for 2. The molecular structures of 1 and 2 revealed the intramolecular aromatic ring stacking between DA and the iodinated phenol ring of Ityr and I(2)tyrO(-), respectively, in correspondence with the solution spectral observations. The stacking with hista was found to be weaker than that with bpy from the interplanar distances in 1 and 2 and the CT band intensities in solution. The molecular and crystal structures revealed some intermolecular iodine-aromatic ring and iodine-oxygen interactions as well as some hydrogen bonds involving the phenol hydroxyl group.
authors.affiliation: Department of Chemistry, Graduate School of Science, Nagoya University, Chikusa-ku, Nagoya 464-01, Japan, and Department of Applied Chemistry, Faculty of Engineering, Nagoya Institute of Technology, Showa-ku, Nagoya 466, Japan.
authors.forename: Feng
authors.initials: F
authors.lastname: Zhang
authors.forename: Tatsuo
authors.initials: T
authors.lastname: Yajima
authors.forename: Hideki
authors.initials: H
authors.lastname: Masuda
authors.forename: Akira
authors.initials: A
authors.lastname: Odani
authors.forename: Osamu
authors.initials: O
authors.lastname: Yamauchi