TY - JOUR
T1 - Structural Dependence of Aromatic Ring Stacking and Related Weak Interactions in Ternary Amino Acid-Copper(II) Complexes and Its Biological Implication
AU - Sugimori, Tamotsu
AU - Masuda, Hideki
AU - Ohata, Nayumi
AU - Koiwai, Kouji
AU - Odani, Akira
AU - Yamauchi, Osamu
PY - 1997/2/12
Y1 - 1997/2/12
N2 - Structures and stabilization due to stacking of ternary copper(II) complexes containing an aromatic amino acid (AA) and an aromatic diamine (DA), Cu(AA)(DA), have been investigated by potentiometric, spectroscopic, and X-ray diffraction methods. For the systems with AA = para-X-substituted L-phenylalanine (L-XPhe; X = H, NO2, OH, NH2) and DA = 2,2′-bipyridine (bpy) or 1,10-phenanthroline (phen), the difference absorption spectra in the region 320-400 nm exhibited a peak assignable to the charge transfer interaction between the aromatic rings of DA and L-XPhe, the intensity being in the order NH2 > OH > H » NO2 with respect to X. The stability constants of Cu(AA)(DA) determined for AA = DL-XPhe (X = F, Cl, Br) and L-XPhe (X = NH2, NO2, I) at 25 °C and I = 0.1 M (KNO3) indicated that stabilization of Cu(L-XPhe)(DA) relative to Cu(L-Ala)(en) (Ala = alanine; en = ethylenediamine) is in the order Br > OH > Cl ≈ NH2 > NO2 ≥ H ≥ F. The structures of [Cu(L-NH2-Phe)(bpy)]NO3·H2O (1), [Cu(L-Tyr)(phen)]ClO4·2.5H2O (2), [Cu(L-Phe)(phen)]Cl·3H2O (3), and [Cu(L-Phe)-(bpy)]ClO4·H2O (4), isolated as crystals, were determined by the X-ray diffraction method: 1, orthorhombic, P212121, a = 10.292(1) Å, b = 13.576(4) Å, c = 14.407(1) Å, V = 2012.9 Å3, Z = 4, R = 0.037, Rw = 0.038; 2, orthorhombic, P212121, a = 18.20(2) Å, b = 32.63(1) Å, c = 8.14(1) Å, V = 4833 Å3, Z = 4, R = 0.111, Rw = 0.087; 3, monoclinic, P21, a = 11.738(2) Å, b = 16.301(1) Å, c = 11.795(1) Å, β = 102.01(1)°, V = 2207.4 Å3, Z = 2, R = 0.045, Rw = 0.035; 4, monoclinic, P21, a = 9.954(2) Å, b = 24.179(3) Å, c = 9.780(2) Å, β = 107.32(1)°, V = 2257.1 Å3, Z = 4, R = 0.065, Rw = 0.060. All of the complexes have a similar distorted square-pyramidal structure around the central Cu(II) ion. While 1 and 2 have a structure involving aromatic ring stacking in the solid state, 4 has a structure without it and 3 has both types of structures in the unit cell.
AB - Structures and stabilization due to stacking of ternary copper(II) complexes containing an aromatic amino acid (AA) and an aromatic diamine (DA), Cu(AA)(DA), have been investigated by potentiometric, spectroscopic, and X-ray diffraction methods. For the systems with AA = para-X-substituted L-phenylalanine (L-XPhe; X = H, NO2, OH, NH2) and DA = 2,2′-bipyridine (bpy) or 1,10-phenanthroline (phen), the difference absorption spectra in the region 320-400 nm exhibited a peak assignable to the charge transfer interaction between the aromatic rings of DA and L-XPhe, the intensity being in the order NH2 > OH > H » NO2 with respect to X. The stability constants of Cu(AA)(DA) determined for AA = DL-XPhe (X = F, Cl, Br) and L-XPhe (X = NH2, NO2, I) at 25 °C and I = 0.1 M (KNO3) indicated that stabilization of Cu(L-XPhe)(DA) relative to Cu(L-Ala)(en) (Ala = alanine; en = ethylenediamine) is in the order Br > OH > Cl ≈ NH2 > NO2 ≥ H ≥ F. The structures of [Cu(L-NH2-Phe)(bpy)]NO3·H2O (1), [Cu(L-Tyr)(phen)]ClO4·2.5H2O (2), [Cu(L-Phe)(phen)]Cl·3H2O (3), and [Cu(L-Phe)-(bpy)]ClO4·H2O (4), isolated as crystals, were determined by the X-ray diffraction method: 1, orthorhombic, P212121, a = 10.292(1) Å, b = 13.576(4) Å, c = 14.407(1) Å, V = 2012.9 Å3, Z = 4, R = 0.037, Rw = 0.038; 2, orthorhombic, P212121, a = 18.20(2) Å, b = 32.63(1) Å, c = 8.14(1) Å, V = 4833 Å3, Z = 4, R = 0.111, Rw = 0.087; 3, monoclinic, P21, a = 11.738(2) Å, b = 16.301(1) Å, c = 11.795(1) Å, β = 102.01(1)°, V = 2207.4 Å3, Z = 2, R = 0.045, Rw = 0.035; 4, monoclinic, P21, a = 9.954(2) Å, b = 24.179(3) Å, c = 9.780(2) Å, β = 107.32(1)°, V = 2257.1 Å3, Z = 4, R = 0.065, Rw = 0.060. All of the complexes have a similar distorted square-pyramidal structure around the central Cu(II) ion. While 1 and 2 have a structure involving aromatic ring stacking in the solid state, 4 has a structure without it and 3 has both types of structures in the unit cell.
UR - http://www.scopus.com/inward/record.url?scp=0000173748&partnerID=8YFLogxK
U2 - 10.1021/ic9608556
DO - 10.1021/ic9608556
M3 - 学術論文
AN - SCOPUS:0000173748
SN - 0020-1669
VL - 36
SP - 576
EP - 583
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 4
ER -