Synthesis, Characterization and Crystal Structure of the First Tri-nuclear MFe_2 (M=Cu and Ni) Compl

• 作 者: 周北川 寇会忠 李勇 熊明 王如骥
• 机 构: Department of Chemistry, Tsinghua University, Beijing 100084, China,Department of Chemistry, Tsinghu
• 出 处: Chinese Journal of Chemistry
• 发表日期: 2003年09期
• 关键词: dimethylamino hydroxyethyl diffractometer Wavelength temper respective coordinat

Three new complexes [Fe(CN) 5(NO)] 2·6H 2O (1), [Fe(CN) 5(NO)] 2·4H 2O (2) and [Fe-(CN) 5(NO)] 2·4H 2O (3) (L=3,10-bis(2-aminoethyl)-1,3,5,8,10,12-hexaazacyclotetradecane) are prepared and characterized by IR, elemental analyses and single-crystal X-ray analyses, indicating that they are the first examples of trinuclear nitroprusside-bridged MFe 2 (M=Cu and Ni) complexes. In the three complexes, the central metal atoms (M) are all six-coordinated by the nitrogen atoms from the macrocyclic ligand and two cyano-bridges at the trans-positions to form distorted octahedral configurations. The axial N-M-N linkage is nearly vertical to the equatorial plane defined by four coordinating N atoms of macrocyclic ligand. The CD-N-Ni bond angle of 172.6° in compleox 1 is apparently larger than those in complexes 2 and 3 (152.57° and 136.37°, respectively). The three complexes are all connected by hydrogen bonds into 3D networks. This study shows that the cyano-bridged trinuclear species could be generated via the control of the charge of the building blocks.

Three new complexes [Fe (CN) 5 (NO)] 2 · 6H 2O (1), [Fe (CN) 5 (NO)] 2 · 4H 2O (2) and [Fe- (CN) 5 2 · 4H 2O (3) (L = 3,10-bis (2-aminoethyl) -1,3,5,8,10,12-hexaazacyclotetradecane) were prepared and characterized by IR, elemental analyzes and single- ray analyzes, indicating that they are the first examples of trinuclear nitroprusside-bridged MFe 2 (M = Cu and Ni) complexes. In the three complexes, the central metal atoms (M) are all six-coordinated by the nitrogen atoms from the macrocyclic ligand and two cyano-bridges at the trans-positions to form distorted octahedral configurations. The axial NMN linkage is nearly vertical to the equatorial plane defined by four coordinating N atoms of the macrocyclic ligand. The C D-N-Ni bond angle of 172.6 ° in compleox 1 is apparently larger than those in complexes 2 and 3 (152.57 ° and 136.37 °, respectively). The three complexes are all connected by hydrogen bonds into 3D networks. This study shows that the cyano-bridged trinuc lear species could be generated via the control of the charge of the building blocks.