Nucleophilic substitution of an iron(II) dichloroclathrochelate with diphenylphosphine sulfide under PTC afforded a monophosphorylated cage complex. This precursor undergoes further nucleophilic substitution with mono- and diamines giving P,N-substituted mono- and bis-clathrochelates; those with thiophosphoryl and pyridyl groups were used as N,S-donor macrobicyclic ligands toward the palladium(II) ion. In the resulting Pd,Fe-binuclear 1 : 1 complexes, the clathrochelate moieties retain the geometry, characteristic of low-spin iron(II) complexes, with a minor distortion caused by intramolecular interactions. The Pd2+ ion has a twisted square-planar N2SCl-environment. The complexes thus obtained proved to be efficient catalysts of the Suzuki cross-coupling reaction.
用
PTC在二
氯氟铵配合物与二苯基
磷硫化物的亲核取代反应中得到了一个单
磷酸化的笼状配合物。该前驱体经过与单胺和双胺的进一步亲核取代,形成 P,N-取代的单笼和双笼配合物;其中带有
硫磷基和
吡啶基的配合物被用作对
钯(II)离子的 N,S-供体大环双环
配体。在所得的 Pd,Fe-双核 1:1 配合物中,笼状配合物的部分保持了低自旋
铁(II)配合物特有的几何形状,仅因分子内相互作用而引起轻微畸变。Pd2+ 离子具有扭曲的方平面 N2SCl 环境。因此得到的配合物被证明是铃木交叉偶联反应的有效催化剂。