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

金属-金属键连接的贵金属卟啉簇复合材料

• 批准号: 15550054
• 负责人: YUGE Hidetaka
• 金额: $ 2.18万
• 依托单位: Kitasato University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2003
• 资助国家: 日本
• 起止时间: 2003 至 2004
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-15550054/
• 关键词: Porphyrin; Ruthenium-Carbon Bond; Osmium-Carbon Bond; Iridium-14 Group Element Bond; Rhodium-14 Group Element Bond; Rhodium-Gold Bond; Crystal Structure; dπ-dπ Interaction; トリフェニルホスフィン; オスミウム; イリジウム-ケイ素結合; ロジウム-ケイ素結合; イリジウム-スズ結合

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.

近年来，人们发展了以金属-金属键连接的卟啉-原子簇复合物，其中以新合成的卡宾钌卟啉和卡宾锇卟啉为例，介绍了金属-碳多重键连接的卟啉簇复合物。在它们的单晶结构中，研究了第六配位位上的刘易斯碱引起的反式影响。在后者中，从锇原子的键长推测了锇原子的氧化态，并在此基础上，发展了含铱-14基团键的化合物。利用金属钾还原生成的铱卟啉阴离子与氯硅烷或氯锡酰反应，合成了一系列化合物。晶体结构分析表明，Ir-Sn和Ir-Si距离小于它们的共价键半径之和。距离缩短的原因可能是由于Ir 5d向Sn 5d或Si 3d轨道的反馈作用产生的dπ-dπ相互作用。紫外<max>-可见光谱中的大ε_和分裂的Soret带明显地反映了dπ-dπ相互作用的影响，从而得到了含铑-金键的化合物。铑卟啉阴离子通过与上述类似的步骤产生，并与金（I）化合物反应。晶体结构分析和光谱测试结果表明，该化合物中存在铑-金键，表明金属卟啉阴离子是形成各种金属-金属键的重要物种。

项目成果

A five-coordinate ruthenium(II)-porphyrin-carbene complex : [bis(3-trifluoromethyl-phenyl)methylene-κC](5,10,15,20-tetra-p-tolylporphyrinato-κ^4N)ruthenium(II)

五配位钌(II)-卟啉-卡宾络合物：[双(3-三氟甲基-苯基)亚甲基-κC](5,10,15,20-四-对甲苯基卟啉-κ^4N)钌(II)

• 发表时间: 2003
• 期刊: Acta Crystallographica Section C 59(9)
• 作者: S.Wada;H.Yuge;T.K.Miyamoto
• 通讯作者: T.K.Miyamoto

S.Wada, H.Yuge, T.K.Miyamoto: "A five-coordinate ruthenium(II)-porphyrin-carbene complex : [bis(3-trifluoromethylphenyl)-methylene-κC](5,10,15,20-tetra-p-tolylporphyrinato-κ^4N)ruthenium(II)"Acta Crystallographica Section C. 59(9). m369-m370 (2003)

S.Wada、H.Yuge、T.K.Miyamoto：“五配位钌(II)-卟啉-卡宾络合物：[双(3-三氟甲基苯基)-亚甲基-κC](5,10,15,20-四-p -甲苯卟啉-κ^4N)钌(II)“晶体学报C.59(9).m369-m370(2003)