Synthesis, Characterization and Crystal Structure of the First Tri-nuclear MFe₂ （M=Cu and Ni） Complexes Based on Nitroprusside

【Abstract】 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.更多还原