SYNTHESIS AND CHARACTERIZATION OF COORDINATION COMPOUNDS OF CHELATING LIGANDS CONTAINING IMIDAZOLE GROUPS. THE CRYSTAL AND MOLECULAR STRUCTURES OF THE DINUCLEAR COPPER(I) AND COPPER(II) COMPOUNDS
SYNTHESIS AND CHARACTERIZATION OF COORDINATION COMPOUNDS OF CHELATING LIGANDS CONTAINING IMIDAZOLE GROUPS. THE CRYSTAL AND MOLECULAR STRUCTURES OF THE DINUCLEAR COPPER(I) AND COPPER(II) COMPOUNDS
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DOI：
10.1002/chin.198242317
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发表时间：
2002-05
期刊：
影响因子：
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通讯作者：
H. Hendriks;P. Birker;J. Rijn;G. Verschoor;J. Reedijk
中科院分区：
文献类型：
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作者：
H. Hendriks;P. Birker;J. Rijn;G. Verschoor;J. Reedijk
阿库! 2（L）（阴离子）2的合成和表征，其中L代表含苯并咪唑的六齿配体之一，N，，′，′-四（2-苯并咪唑甲基）-1，2-乙二胺（缩写为EDTB）、A7、A'、A''、Av-四[（1-甲基-2-苯并咪唑基）甲基]-1，2-乙二胺（NMEDTB），2-乙二胺（NBEDTB）、N，N ′，N ′-四[（5-甲基-2-苯并咪唑基）甲基]-1，2-乙二胺（5-MEDTB）或N，N ′，N ′-四[（5，6-二甲基-2-苯并咪唑基）甲基]-1，2-乙二胺（5，6-DMEDTB）。组成为Cu（L）（阴离子）_2的所有化合物的电子和ESR谱与Cu（EDTB）（阴离子）_2的电子和ESR谱相同，并表明其结构类似于Cu（EDTB）（BF_4）（BF_3OC_2H_5）的结构，被描述为高度扭曲的正方形金字塔。化合物Cu_2（L）（阴离子）_4的ESR和电子光谱表明，在不同阴离子存在下具有不同的配位几何构型。在含Cl-或Br-的化合物中，Cu 11原子似乎具有三角-双锥配位几何结构。对于化合物Cu2（L）X4，四方锥几何形状似乎更可能，其中X = NO3-、BF 4-或C104-。用单晶X射线衍射法测定了[Cu~（2+）（NMEDTB）（NO_3）_3] NO_3·4H_（20）（1）和Cu~（2+）（EDTB）（C_（10）_4）_2（2）的晶体和分子结构。这两种化合物均以空间群C2/c结晶。对于化合物1，a = 19.159（4）λ，B = 15.907（2）λ，c = 16.816（3）λ，λ = 109.57（2）λ，V = 4829.0 λ 3，Z = 4，θ measd = 1.51（1）g cm-3，和θ c4 lcd = 1.49 g cm-3。在自动衍射仪上测量4241个独立反射的强度，其中2670个被认为是观察到的（I> 2（））。对于化合物2，a = 13.849（2）A，B = 18.913（2）A，c = 14.062（2）A，0 = 102.10（1），V = 3592.2 A3，Z = 4，μ mcasd = 1.65（1）g cm-3，和μ mcasd = 1.68 g cm-3。总共测量了3522个独立的反射，其中2627个被认为是观察到的。这两种结构都通过重原子方法求解，并通过使用最小二乘法进行精修，得到1的残余R值为0.046，2的残余R值为0.039。结构1由具有C2对称性的双核Cu 2（NMEDTB）（NO3）3+阳离子、无序硝酸根离子和无序水分子组成。每个铜离子周围的配位几何形状可以被描述为具有两个赤道苯并咪唑氮原子、一个赤道胺氮原子、一个单齿配位硝酸根离子的赤道氧原子和一个桥连到阳离子中的另一个铜离子的轴向位置的硝酸根离子的轴向氧原子的四方锥。结构2由具有C2对称性的双核Cu '2（EDTB）2+阳离子和高氯酸根离子组成。每个铜原子与两个苯并咪唑氮原子呈线性配位，铜-氮短键分别为1.869（4）和1.876（4）。单位内Cu-Cu距离为3.043（1）A。Cu ′ 2（EDTB）2+离子的结构与最近提出的血蓝蛋白还原态模型非常相似。化合物Cu '2（L）2+确实以1：1摩尔比与O2反应，但不能分离出O2加合物。
Cu! 2 (L)(anion) 2 have been prepared and characterized, where L stands for one of the sexadentate benzimidazole-containing ligands N,,','-tetrakis (2-benzimidazolylmethyl)-l, 2-ethanediamine (abbreviated EDTB), A7, A', A’', Av-tetrakis [(1-methyl-2-benzimidazolyl) methyl]-l, 2-ethanediamine (NMEDTB), Ar, 7V,/V,, Ar,-tetrakis [(l-benzyl-2-benzimidazolyl)-methyl]-!, 2-ethanediamine (NBEDTB),,'", A'-tetrakis [(5-methyl-2-benzimidazolyl) methyl]-l, 2-ethanediamine (5-MEDTB), or N, N,', 7V'-tetrakis [(5, 6-dimethyl-2-benzimidazolyl) methyl]-l, 2-ethanediamine (5, 6-DMEDTB). The electronicand ESR spectra of all compounds of composition Cun (L)(anion) 2 are identical with those for Cu (EDTB)(anion) 2 and suggest a structure similar to the one found for Cu (EDTB)(BF4)(BF3OC2H5), which has been described as highly distorted square pyramid. ESR and electronic spectra of the compounds Cu2 (L)(anion) 4 indicate different coordination geometries in the presence of different anions. In compounds with Cl" or Br" the Cu11 atom appears to have trigonal-bipyramidal coordination geometry. Square-pyramidal geometry seems more likely for compounds Cu2 (L) X4, where X= N03", BF4", or C104". Thecrystal and molecular structures of [Cun2 (NMEDTB)(N03) 3] N03-4H20 (1) and of Cu* 2 (EDTB)(C104) 2 (2) have been determined by single-crystal X-ray analysis. Both compounds crystallize in space group C2/c. For compound 1, a= 19.159 (4) Á, b= 15.907 (2) Á, c= 16.816 (3) A, ß= 109.57 (2), V= 4829.0 Á3, Z= 4, 0measd= 1.51 (1) g cm" 3, and 0c4lcd= 1.49 g cm" 3. The intensities of 4241 independent reflections were measured on an automatic diffractometer, 2670 of which were considered as observed (I> 2 ()). For compound 2, a= 13.849 (2) A, b= 18.913 (2) A, c= 14.062 (2) A, 0= 102.10 (1), V= 3592.2 A3, Z= 4,¿ mcasd= 1.65 (1) g cm" 3, and= 1.68 g cm" 3. A total of 3522 independent reflections were measured, 2627 of which were considered as observed. Both structures were solved by heavy-atom methods and refined by using least-squares techniques to a residual R value of 0.046 for 1 and 0.039 for 2. Structure 1 consists of dinuclear Cu2 (NMEDTB)(N03) 3+ cations having C2 symmetry, a disordered nitrate ion, and disordered water molecules. The coordination geometry around each copper ion can be described as square pyramidal with two equatorial benzimidazole nitrogenatoms, one equatorial amine nitrogen atom, one equatorial oxygen atom of a monodentate coordinating nitrate ion, and one axial oxygen atom of a nitrate ion which is bridging to the axial position of the other copper ion in the cation. Structure 2 consists of dinuclear Cu’2 (EDTB) 2+ cations having C2 symmetry and perchlorate ions. Each copper is linearly coordinatedby two benzimidazole nitrogen atoms, with short Cu-N bonds of 1.869 (4) and 1.876 (4) A, respectively. The Cu-Cu distance within one unit is 3.043 (1) A. The structure of the Cu'2 (EDTB) 2+ ion shows a strong resemblance with a recently proposed model for the reduced state of hemocyanin. The compounds Cu'2 (L) 2+ do react with 02 in a 1: 1 molar ratio although no 02 adducts could be isolated.