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

(1)过渡金属-磷配合物研究。研究了以二氨基取代亚磷酸酯为配体的Lewis酸6族过渡金属配合物合成磷配合物的新途径。根据得到的金属-磷配合物的反应活性、各种光谱数据、取代基对稳定性的影响和x射线结构，估计了P-M键的双键特征。相应的铁配合物（8族）与路易斯酸发生类似但有趣的反应。即与铁原子配位的14基团元素配体ER_3为烷基时，易于向磷配体迁移，而当ER_3为硅基或香豆基时，则不发生这种迁移，且磷配合物是可分离的。另一方面，ER_3作为一个锡基得到了一个锡炔配合物，其中Sn原子上的烷基而不是锡基本身迁移到磷配体上。(2)磷烷配合物的研究。含有三苯基亚磷酸酯的铁配合物通过与一些路易斯碱反应转化为铁-磷烷配合物，其中P原子的价扩展到5。根据其光谱数据和x射线结构，声称铁碎片作为高价P原子的pi电子供体。这些化合物的伪旋转特性也通过变温核磁共振检查。(3)磷酸环配合物的研究。利用模板反应制备了Pd和Pt与14元和16元磷环木质素配合物。这些配合物的x射线结构显示，14元磷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.