Stepwise and Self-Assembly Synthesis of Tetranuclear Iron-Thiolate-Diisocyanide Metallocyclophane Complexes

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• 作者：Yen-Chung Huang ; Hsuan-Ying Chen ; Chau-Yu Cheng ; Yu-Lin Tsai ; Michael Y. Chiang and Sodio C. N. Hsu
• 刊名：Journal of the Chinese Chemical Society
• 出版年：2017
• 出版时间：January 2017
• 年：2017
• 卷：64
• 期：1
• 页码：94-102
• 全文大小：513K
• ISSN：2192-6549

文摘

Treatment of known complex [Cp₂Fe₂ (μ-SEt)₂(CH₃CN)₂](BF₄ )₂ (1(BF₄ )₂) with 2 equiv of 1,4-bis(isocyanomethyl)benzene (1,4-CNCH₂C₆H₄CH₂NC; L1 ) or 4,4′-diisocyanophenyl ether (4,4′-CNC₆H₄OC₆H₄NC; L2 ) result in the formation of two new-type diisocyanide complexes [Cp₂Fe₂ (μ-SEt)₂(1,4-CNCH₂C₆H₄CH₂NC)₂](BF₄ )₂ (2a(BF₄ )₂) or [Cp₂Fe₂ (μ-SEt)₂(4,4′-CNC₆H₄OC₆H₄NC)₂](BF₄ )₂ (2b(BF₄ )₂), respectively. The new-type 24-membered ring tetranuclear iron–thiolate–aryldiisocyanide metallocyclophane complex [Cp₄Fe₄ (μ-SEt)₄(μ-1,4-CNCH₂C₆H₄CH₂NC)₂](BF₄ )₄ (3a(BF₄ )₄) has been synthesized by using a self-assembly reaction between equimolar amounts of 1(BF₄ )₂ and 1,4-bis(isocyanomethyl)benzene or by a stepwise route involving mixing a 1:1 molar ratio of complexes 1(BF₄ )₂ and 2a(BF₄ )₂. A similar approach was used through the application of equal molar ratio of complexes 1(BF₄ )₂ and 2b(BF₄ )₂ to give a 30-membered ring tetranuclear iron–thiolate–aryldiisocyanide metallocyclophane complex [Cp₄Fe₄ (μ-SEt)₄(4,4′-CNC₆H₄OC₆H₄NC)₂][BF₄ ]₄ (3b(BF₄ )₄). The spectroscopic and electrochemical properties of four iron–sulfur core complexes were determined.