Preparation, Structures, and Reactivities of Metal Complexes Bearing a Variety of Bonding Modes between Phosphorus Compounds and Transition Metals.

(1)过渡金属-膦配合物的研究以二氨基取代的亚磷酸酯为配体的第6族过渡金属配合物为原料，用刘易斯酸处理，发展了一条合成膦配合物的新路线。根据反应活性、各种光谱数据、取代基对稳定性的影响以及所得金属-膦配合物的X-射线结构，估计了所得P-M键中的双键特征.相应的铁（第8族）配合物与刘易斯酸发生类似但有趣的反应.也就是说，当与铁原子配位的14族元素配体ER_3是烷基时，它容易迁移到膦配体，而当ER_3基团是甲硅烷基或甲锗烷基时，这种迁移不发生，并且膦络合物是可分离的。当ER_3为锡烷基时，则得到锡烯配合物，其中锡原子上的烷基迁移到膦配体上，而锡烷基本身不迁移到膦配体上。(2)磷烷配合物的研究含亚磷酸三苯酯的铁配合物通过与某些刘易斯碱反应转化为铁-磷烷配合物，其中P原子的化合价扩展到5。根据它的光谱数据和X射线结构，有人声称，铁片段作为一个π电子供体的h超价P原子。这些化合物的赝旋光特性也通过变温核磁共振进行了研究。(3)磷杂大环配合物的研究利用模板反应合成了14元和16元磷杂大环配体的钯、铂配合物。这些配合物的X-射线结构表明，14元磷杂环配体的空穴不足以形成较少约束的金属配合物。

(1) Study on Transition Metal-Phosphenium Complexes.A new synthetic route to phosphenium complexes was developed treating with a Lewis acid a group 6 transition metal complex having a diamino-substituted phosphite as a ligand. A double bond character in the resulting P-M linkage was estimated on the basis of the reactivities, various spectroscopic data, substituent effect on the stability, and X-ray structures of the metal-phosphenium complexes thus obtained.The corresponding complexes of iron (group 8) undergo similar but interesting reaction witha Lewis acid. That is, when the 14 group element ligand ER_3 coordinated to the iron atom is an alkyl group, it readily migrates to the phosphenium ligand, while such migration does not take place and the phosphenium complex is isolable when the ER_3 group is a silyl or germyl group. On the other hand, a stannylene complex is obtained for ER_3 being a stannyl group, where the alkyl group on the Sn atom but not the stannyl group itself migrates to the phosphenium ligand.(2) Study on Phosphorane Complexes.The iron complex having a triphenylphosphite is converted into the iron-phosphorane complex by the reaction with some Lewis bases, where the valency of the P atom is expanded to five. On the basis of its spectroscopic data and X-ray structures, it is claimed that the iron fragment acts as a pi-electron donor to the hhypervalent P atom. The pseudorotation characteristic of these compounds is also examined by variable temperature NMR.(3) Study on Phosphamacrocycle Complexes.Pd and Pt complexes with 14- and 16-membered phosphamacocyclic lignads were prepared by utilizing the template reaction. X-ray structures of these complexes revealed that the hole of the 14-membered phosphamacocyclic ligands is not sufficiently large to form less-constrained metal complexes.