Deters Elizabeth A, Goldcamp Michael J, Krause Bauer Jeanette A, Baldwin Michael J
Department of Chemistry, University of Cincinnati, Cincinnati, Ohio 45221-0172, USA.
Inorg Chem. 2005 Jul 25;44(15):5222-8. doi: 10.1021/ic048355x.
Two new ligands consisting of bis(oxime) amine units tethered by a bridge have been synthesized. Their nickel chloride and nickel nitrate complexes have also been synthesized and characterized by X-ray crystallography, FTIR, mass spectrometry, and elemental analysis. One of these ligands, L1 (N,N,N',N'-tetra(1-propan-2-onyl oxime)-diamino-m-xylene), is always dinucleating, while the other ligand, L2 (N,N,N',N'-tetra(1-propan-2-onyl-oxime)-1,3-diaminopropane), shows an unusual anion dependence on the nuclearity. When nickel chloride is used, the ligand acts in a dinucleating manner and coordinates two nickels; however, when nickel nitrate is used, the ligand acts in a monodentate fashion and coordinates only one nickel. Once the mononuclear complex is formed, it is not possible to add a second nickel if Ni(NO(3))(2) is used as the nickel source; it is possible, however, to add a second nickel if NiCl(2) is used as the nickel source. The dinuclear complex can be converted to the mononuclear one by either using silver nitrate to exchange the chloride anions for nitrates or by dissolving the complex in water. Ni(2)(L1)Cl(4)(DMF)(2).DMF: orthorhombic, P2(1)2(1)2(1), a = 12.2524(11) A, b = 16.6145(15) A, c = 20.1234(19) A, V = 4096.5(6) A(3), Z = 4. Ni(2)(L2)Cl(4)(DMF).2DMF: triclinic, P-1, a = 12.5347(5) A, b = 12.5403(5) A, c = 14.3504(6) A, alpha = 67.348(1) degrees , beta = 69.705(1) degrees , gamma = 81.549(1) degrees , V = 1952.25(14) A(3), Z = 1. Ni(L2).(NO(3))(2): monoclinic, P2(1)/n, a = 9.6738(3) A, b = 30.2229(9) A, c = 15.8238(5) A, beta = 97.995(1) degrees , V = 4581.4(2) A(3), Z = 8.
合成了两种由桥连的双（肟）胺单元组成的新型配体。还合成了它们的氯化镍和硝酸镍配合物，并通过X射线晶体学、傅里叶变换红外光谱、质谱和元素分析对其进行了表征。其中一种配体L1（N，N，N'，N'-四（1-丙-2-酮肟基）-二氨基间二甲苯）总是双齿配位的，而另一种配体L2（N，N，N'，N'-四（1-丙-2-酮肟基）-1，3-二氨基丙烷）对核数表现出不寻常的阴离子依赖性。当使用氯化镍时，该配体以双齿配位方式作用并配位两个镍；然而，当使用硝酸镍时，该配体以单齿方式作用且仅配位一个镍。一旦形成单核配合物，如果使用Ni(NO₃)₂作为镍源，则不可能添加第二个镍；但是，如果使用NiCl₂作为镍源，则可以添加第二个镍。通过使用硝酸银将氯离子交换为硝酸根离子或将配合物溶解在水中，双核配合物可以转化为单核配合物。Ni₂(L1)Cl₄(DMF)₂·DMF：正交晶系，P2₁2₁2₁，a = 12.2524(11) Å，b = 16.6145(15) Å，c = 20.1234(19) Å，V = 4096.5(6) ų, Z = 4。[Ni₂(L2)Cl₄(DMF)]₂·2DMF：三斜晶系，P-1，a = 12.5347(5) Å，b = 12.5403(5) Å，c = 14.3504(6) Å，α = 67.348(1)°，β = 69.705(1)°，γ = 81.549(1)°，V = 1952.25(14) ų，Z = 1。Ni(L2)(NO₃)₂：单斜晶系，P2₁/n，a = 9.6738(3) Å，b = 30.2229(9) Å，c = 15.8238(5) Å，β = 97.995(1)°，V = 4581.4(2) ų，Z = 8。
