Luo Hongyan, Lo Jem-Mau, Fanwick Phillip E., Stowell Joseph G., Green Mark A.
Department of Medicinal Chemistry and Molecular Pharmacology and Department of Chemistry, Purdue University, West Lafayette, Indiana 47907-1333.
Inorg Chem. 1999 May 3;38(9):2071-2078. doi: 10.1021/ic981324f.
A convenient four-step procedure was developed to prepare the novel monoprotic tetradentate ligands N-(2-hydroxy)benzyl-N-methyl-N'-(2-pyridyl)methyl-1,3-propanediamine (Hpamap) and N-(2-hydroxy)benzyl-N'-methyl-N'-(2-pyridyl)methyl-1,3-propanediamine (Hpmaap), which provide an N(3)O metal coordination sphere. A mononuclear copper(II) complex, [Cu(pamap)Cl] (A), was obtained by reaction of Hpamap with CuCl(2).2H(2)O. The binuclear copper(II) complexes Cu(pamap)(BF(4))(2) (B) and Cu(pmaap)(BF(4))(2) (C) were obtained when these ligands were reacted with Cu(II) in the presence of the noncoordinating BF(4)(-) anion. Reaction of nickel(II) with the Hpamap ligand generated the binuclear Ni(II) complex [Ni(2)(pamap)(2)(NO(3))]NO(3) (D). The crystal of A (C(17)H(22)ClCuN(3)O) is orthorhombic Pbca (No. 61), a = 11.837(4) Å, b = 15.648(5) Å, c = 11.002(11) Å, Z = 8; that of B (C(34)H(44)B(2)Cu(2)F(8)N(6)O(2)) is triclinic P&onemacr; (No. 2), a = 9.147(0) Å, b = 10.375(0) Å, c = 10.535(1) Å, alpha = 107.20(0) degrees, beta = 91.19(0) degrees, gamma = 105.05(0) degrees, Z = 1; that of C (C(34)H(44)B(2)Cu(2)F(8)N(6)O(2)) is monoclinic P2(1)/c (No. 14), a = 9.158(2) Å, b = 10.714(2) Å, c = 19.085(4) Å, beta = 90.58(2) degrees, Z = 4; and that of D (C(34)H(44)N(8)NiO(8)) is monoclinic C2/c (No. 15), a = 13.849(0) Å, b = 13.609(0) Å, c = 19.558(1) Å, beta = 92.34 (0) degrees, Z = 4. The copper atoms of all three complexes are five-coordinate in the solid state, assuming the geometry of a distorted square pyramid with the deprotonated tetradentate ligand in the basal plane. The mononuclear complex A has a chloride ligand in the axial position, while each copper center in the binuclear complexes B and C has, in the axial position, a bridging phenolate O donor from the other unit of the dimer. Each nickel center in the binuclear complex D is six-coordinate, with the pseudo-octahedron formed by a deprotonated tetradentate ligand, a bridging nitrato oxygen atom, and a bridging phenoxy donor from the tetradentate ligand bound to the second nickel center.
已开发出一种简便的四步程序来制备新型单质子四齿配体N-(2-羟基)苄基-N-甲基-N'-(2-吡啶基)甲基-1,3-丙二胺(Hpamap)和N-(2-羟基)苄基-N'-甲基-N'-(2-吡啶基)甲基-1,3-丙二胺(Hpmaap)，它们提供一个N(3)O金属配位球。通过使Hpamap与CuCl₂·2H₂O反应得到单核铜(II)配合物Cu(pamap)Cl。当这些配体在非配位的BF₄⁻阴离子存在下与Cu(II)反应时，得到双核铜(II)配合物[Cu(pamap)]₂(BF₄)₂(B)和[Cu(pmaap)]₂(BF₄)₂(C)。镍(II)与Hpamap配体反应生成双核Ni(II)配合物[Ni₂(pamap)₂(NO₃)]NO₃(D)。A(C₁₇H₂₂ClCuN₃O)的晶体为正交晶系Pbca(编号61)，a = 11.837(4) Å，b = 15.648(5) Å，c = 11.002(11) Å，Z = 8；B(C₃₄H₄₄B₂Cu₂F₈N₆O₂)的晶体为三斜晶系P&onemacr;(编号2)，a = 9.147(0) Å，b = 10.375(0) Å，c = 10.535(1) Å，α = 107.20(0)°，β = 91.19(0)°，γ = 105.05(0)°，Z = 1；C(C₃₄H₄₄B₂Cu₂F₈N₆O₂)的晶体为单斜晶系P2(1)/c(编号14)，a = 9.158(2) Å，b = 10.714(2) Å，c = 19.085(4) Å，β = 90.58(2)°，Z = 4；D(C₃₄H₄₄N₈NiO₈)的晶体为单斜晶系C2/c(编号15)，a = 13.849(0) Å，b = 13.609(0) Å，c = 19.558(1) Å，β = 92.34(0)°，Z = 4。所有三种配合物的铜原子在固态下均为五配位，呈扭曲的四方锥几何构型，去质子化的四齿配体位于底面。单核配合物A在轴向位置有一个氯配体，而双核配合物B和C中的每个铜中心在轴向位置有一个来自二聚体另一单元的桥连酚氧供体。双核配合物D中的每个镍中心为六配位，由去质子化的四齿配体、一个桥连硝酸根氧原子和一个来自与第二个镍中心相连的四齿配体的桥连苯氧基供体形成伪八面体。
