Precious Metal Porphyrin-Cluster Composites Linked with Metal-Metal Bonds

以金属-金属键连接的卟啉簇复合材料已被开发出来。初步合成了含金属-碳多键的碳钌卟啉和碳锇卟啉。在它们的单晶结构中，研究了六配位位路易斯碱对其反式的影响。在后者中，锇原子的氧化状态由它们的键长推测出来。在此基础上，开发了含铱-14基团的化合物。以金属钾还原生成的卟啉铱阴离子与氯化硅或氯化锡反应，合成了一系列化合物。晶体结构分析表明，Ir-Sn和Ir-Si的距离小于它们的共价键半径之和。缩短的距离可能是由于Ir - 5d轨道与Sn - 5d或Si - 3d轨道的反向赋能导致的dπ-dπ相互作用。紫外-可见光谱中较大的ε_<max>和分裂的Soret带明显显示了dπ-dπ相互作用的影响。研制了含铑金键的复合材料。卟啉铑阴离子由与上述类似的过程生成，并与金(I)化合物反应。晶体结构分析和光谱测量结果表明，该化合物具有铑-金键。研究表明，金属卟啉阴离子是形成各种金属-金属键的非常有用的种类。

Porphyrin-cluster composites linked with metal-metal bond have been developed.Preliminarily carbene ruthenium porphyries and carbene osmium porphyrins were newly synthesized as examples involving metal-carbon multiple bond. In their single crystal structures of the formers the trans influence caused by the Lewis base at the sixth coordination site was investigated. In the latter the oxidization state of the osmium atom was speculated from their bond lengths.Based on the above, the compounds bearing iridium-14 group bond have been developed. A series of compounds were synthesized by reactions of iridium porphyrin anions, generated by reduction using potassium metal, with silyl chloride or stannyl chloride. Crystal structure analysis revealed that Ir-Sn and Ir-Si distances were shorter than the sums of their covalent bond radii. The shortened distances would be due to the dπ-dπ interactions by the back-donation from the Ir 5d to Sn 5d or Si 3d orbitals. The large ε_<max> and the split Soret band in the UV-Vis spectra evidently show the influences of the dπ-dπ interactions.The compound bearing rhodium-gold bond has been developed. The rhodium porphyrin anion was generated by a similar procedure to the above and reacted with a gold(I) compound. Results of the crystal structure analysis and spectroscopic measurements shows that the compound had a rhodium-gold bond.The investigations demonstrated the metalloporphyrin anions were very useful species for the formation of various metal-metal bonds.