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

点击翻译按钮获取中文摘要

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.