[38]Octaphyrin bis-Sn(IV) complexes with unique coordination geometries
[38]Octaphyrin bis-Sn(IV) complexes with unique coordination geometries
复制标题
[38]具有独特配位几何形状的八菲林双-Sn(IV)配合物
DOI：
10.1142/s1088424621500103
复制
发表时间：
2021
期刊：
影响因子：
--
通讯作者：
A. Osuka
中科院分区：
文献类型：
--
作者：
M. Izawa;A. Nakai;T. Suito;T. Tanaka;A. Osuka
八氢呋喃(1.1.1.1.1.1.1.1)的金属络合作用可触发独特的固环能力或意外的重排(裂解)反应。本文研究了[38]八氢吡喃与锡(IV)金属络合的独特行为。分离得到两个新的[38]八氢吡喃双锡(IV)配合物2Sn2和3Sn2，其性质为弱芳香分子。具有分子对称性的2Sn2与已报道的八氢吡喃双硅(IV)和双Ge(IV)配合物具有相似的特征，而3Sn3则表现出一种不同的配位模式，即通过吡咯酸NH与TiN离子上的轴向连接的羟基之间的分子内氢键固定。在尝试生长2Sn晶体的过程中，还观察到了意想不到的二聚体结构。这些特征行为表明，即使对于相同的14族元素，八氢吡喃的固环能力对金属离子的性质也相当敏感。
Metal complexation of octaphyrin(1.1.1.1.1.1.1.1) triggers unique ring-fixation aptitudes or unexpected rearrangement (cleavage) reactions. In this paper, a unique complexation behavior of [38]octaphyrin upon tin(IV) metalation is showcased. Two new [38]octaphyrin bis-Sn(IV) complexes2Snand3Snwere isolated and characterized as weakly aromatic molecules. While2Snwith themolecular symmetry displayed a similar characteristic to octaphyrin bis-Si(IV) and bis-Ge(IV) complexes reported previously,3Snshowed a different coordination mode that is fixed by intramolecular hydrogen bondings between pyrrolic NH and axially ligated OH on the tin ion as revealed by X-ray diffraction analysis. An unexpected dimeric structure was also observed during an attempt to grow crystals of2Sn. These characteristic behaviors indicate that the ring-fixation aptitude of octaphyrin is quite sensitive to the nature of metal ions even for the same group 14 elements.