Structure of an iron(II) complex with a novel sexadentate ligand derived from a tetraaza macrocycle
Structure of an iron(II) complex with a novel sexadentate ligand derived from a tetraaza macrocycle
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具有源自四氮杂大环的新型六齿配体的铁（II）络合物的结构
DOI：
10.1021/ic50178a049
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发表时间：
1977
期刊：
影响因子：
--
通讯作者：
D. H. Busch
中科院分区：
文献类型：
--
作者：
K. B. Mertes;P. Corfield;D. H. Busch
最近的一系列低自旋铁（II）配合物与大环配体的调查已经产生了一个新的sexadentate铁（II）螯合物形成的亲电攻击的两个协调的乙腈分子在顶端碳的母大环。以这种方式，乙腈形成附加的亚氨基乙基基团，其很好地定向用于螯合。三维X射线晶体结构测定证实并阐明了配合物顺式-3，11-双的独特性质（1-亚氨基乙基-2，12-二甲基-1，5，9，13-四氮杂环十六碳-1，4，9，12-四烯铁（II）六氟磷酸盐以正交晶系空间群i ′ 2，2121结晶，晶胞尺寸a= 21.647（19），B= 11.077（11）和c= 11.115（9）π。用傅里叶变换和最小二乘法对2787个反射峰进行了解析，得到了R= 0.064的结果。六个氮原子形成一个略微扭曲的三角八面体，铁氮原子的距离从1.936到1.971 <$。平均CN键长为1.256 nm，与这些环中的双键定位一致。因此，配位层由六个亚胺氮供体组成。大环是折叠的，亚氨基乙基的氮在顺式位置配位。
Recent investigations of a series of low-spin iron (II) complexes with macrocyclic ligands have yielded a new sexadentate iron (II) chelate formed by the electrophilic attack of two coordinated acetonitrile molecules at the apical carbons of the parent macrocycles. In this way the acetonitriles form appended iminoethyl groups that are well oriented for chelation. A three-dimensional x-ray crystallographic structural determination has confirmed and clarified the unique nature of the complex, cis-3, 11-Bis (l-iminoethyl-2, 12-dimethyl-1, 5, 9, 13-tetraazacyclohexadeca-1, 4, 9, 12-tetraeneiron (II) hexafluorophosphate crystallizes in the orthorhombic space group/’2, 2121 with cell dimensions a= 21.647 (19), b= 11.077 (11), and c= 11.115 (9) Á. The structure was solved byFourier and least-squares techniques to a conventional R= 0.064 for 2787 reflections. The six nitrogens form a slightly trigonal distorted octahedronand the iron nitrogendistances vary from 1.936 to 1.971 Á. The average CN bond length of 1.256 Á coincides with double bond localization in these rings. The coordination sphere therefore consists of six imine nitrogen donors. The macrocycle is folded and the nitrogens of the iminoethyl groups are coordinated in cis positions.