Construction and Function of One-dimensional Organometallic Composites Consisting of π-Conjugated Molecule and Metal Chain

π共轭分子与金属链组成的一维有机金属复合材料的构建与功能

• 批准号: 13450370
• 负责人: KUROSAWA Hideo
• 金额: $ 7.49万
• 依托单位: Osaka University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 2001
• 资助国家: 日本
• 起止时间: 2001 至 2002
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-13450370/
• 关键词: Cluster-comlex; sandwich-complex; palladium complex; polyene; 光異性化; テトラエン錯体; 3核錯体; パラジウムクラスター; 一次元化合物; 有機金属錯体

Great attention has been paid to π-conjugated molecules such as polyacetylenes and polyphenylenes as functional organic materials, while one-dimensional polymetal wires also attract attention as inorganic functional materials and catalysts. The objective of the current project is to construct linear organometallic composites by combining these organic and inorganic conjugate systems via coordination bond, and to examine their catalytic and electric properties for application to the functional composites.We first attained the synthesis of Pd-Pd bonded complex containing six acetonitrile ligands, which suit for substitution by rather weakly coordinating unsaturated hydrocarbon ligands. This Pd-Pd complex reacted with 1,6-diphenylhexatriene to give sandwich complex in which two hexatriene ligands coordinate with the Pd-Pd moiety. The structure of the new sandwich complex was determined by X-ray crystallography. The reaction of a given polyene (double bond number = n) with acetonitrile Pd-Pd complex in the presence of n-3 equivalent Pd(0) afforded linear sandwich complex composed of (Pd)n-1 chain and two polyene ligands.We also found that photo-irradiation (>510 nm) at room temperature of Pd3-tetraene sandwich complex induces interconversion between meso and racemi isomers of this sandwich complex, while no such interconversion takes place under dark at room temperature. Treatment of the Pd3 sandwich with reducing or oxidizing reagent led to no similar isomerization.

聚乙炔、聚苯乙烯等π共轭分子作为功能有机材料受到了极大的关注，而一维多金属丝作为无机功能材料和催化剂也受到了人们的关注。本课题的目标是通过配位键将这些有机和无机共轭体系结合，构建线性有机金属复合材料，并研究其催化性能和电学性能，以应用于功能复合材料。我们首次合成了含有6个乙腈配体的Pd-Pd键配合物，该配合物适合被配位较弱的不饱和烃配体取代。该Pd-Pd配合物与1,6-二苯基己三烯反应生成夹层配合物，其中两个己三烯配体与Pd-Pd部分配位。用x射线晶体学测定了新夹层配合物的结构。给定多烯（双键数= n）与乙腈Pd-Pd配合物在n-3等量Pd(0)存在下反应得到由（Pd）n-1链和两个多烯配体组成的线性夹心配合物。我们还发现，pd3 -四烯夹层配合物在室温下的光照射（>510 nm）诱导了该夹层配合物的中消旋异构体和外消旋异构体之间的相互转化，而在室温下的暗照射下则没有发生这种相互转化。用还原剂或氧化剂处理过的Pd3夹层没有类似的异构化反应。

项目成果

T.Murahashi, Y.Higuchi, T.Kato, H.Kurosawa: "Photo-induced Face-Inversion of Conjugated Tetraene Ligands on a Pd-Pd-Pd Moiety"J. Am. Chem. Soc.. 124. 14288-14289 (2002)

T.Murahashi、Y.Higuchi、T.Kato、H.Kurosawa：“Pd-Pd-Pd 部分上共轭四烯配体的光诱导面反转”J。

T.Murahashi, T.Nagai, Y.Mino, E.Mochizuki, Y.Kai, H.Kurosawa: "Reversible Interconversion between Pinuclear Sandwich and Half-Sandwich Completes, Unique Dynamic Behavior of a Pd-Pd Moiety Surrounded by an SP^2 Carbon Framework"J. Am. Chem. Soc.. 123. 6927

T.Murahashi、T.Nagai、Y.Mino、E.Mochizuki、Y.Kai、H.Kurosawa：“松核三明治和半三明治之间的可逆相互转换完成，被 SP 包围的 Pd-Pd 部分的独特动态行为^

T.Murahashi, H.Kurosawa: "Organopalladium Complexes Containing Palladium-Palladium Bonds"Coord.Chem.Rev.. 231. 207-228 (2002)

T.Murahashi、H.Kurosawa：“含有钯-钯键的有机钯配合物”Coord.Chem.Rev.. 231. 207-228 (2002)

H.Kurosawa, 他3名: "Photo-induced Face Inversion of Conjugated Tetracne Ligands on a Pd-Pd-Pd Moiety"J.Am.Chem.Soc. 124. 14288-14289 (2002)

H.Kurosawa 等 3 人：“Pd-Pd-Pd 部分上的共轭四烯配体的光诱导面反转”J.Am.Chem.Soc. 124. 14288-14289 (2002)

T.Murahashi, H.Kurosawa: "Organopalladium Complexes Containing Palladium-Palladium Bonds"Coord. Chem. Rev.. 231. 207-228 (2002)

T.Murahashi、H.Kurosawa：“含有钯-钯键的有机钯配合物”坐标。