Bis(bismuth)toluene Inverted-Sandwich Complex Supported by Aminetris(phenoxide) Ligands

The reaction of bismuth amides or alkoxides with phenolic ligand
precursors yields Bi complexes of aminetris(phenoxide)s, one of
which was characterized by X-ray crystallography, revealing
monomeric Bi units of the tetradentate NO3 ligand further associated
via a symmetrical toluene bridge into a bis(bismuth)toluene inverted-sandwich complex. Synthesis of the analogous Sb complex
suggests a markedly different geometric and electronic environment
at the metal center, as evidenced by the solid-state molecular
structure. Density functional theory calculations of the sandwich
bismuth arene complex indicate the presence of a weak σ*−2π
interaction.

铋酰胺与醇盐分别或共同与酚类配体前体反应，可生成氨基三(酚氧基)配体修饰的铋配合物。其中一种配合物经X射线晶体衍射（X-ray crystallography）表征，结果显示其包含四齿NO3配体的单核铋单元，该单元通过对称甲苯桥进一步缔合，形成双铋甲苯反三明治配合物。针对类似锑配合物的合成研究表明，金属中心的几何与电子环境存在显著差异，该结论可通过固态分子结构得到验证。对该三明治型铋芳烃配合物的密度泛函理论（Density functional theory）计算结果显示，体系中存在弱σ*−2π相互作用。