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

作者：Huang, Yen Chung; Chen, Hsuan Ying; Cheng, Chau Yu; Tsai, Yu Lin; Chiang, Michael Y; Hsu, Sodio C N

来源：Journal of the Chinese Chemical Society, 2017, 64(1): 94-102.

DOI：10.1002/jccs.201600776

• Stepwise formation
• Self-assembly
• Isocyanide
• Electrochemistry

Treatment of known complex [Cp2Fe2(mu-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(mu-SEt)(2)(1,4-CNCH2C6H4CH2NC)(2)](BF4)(2) (2a(BF4)(2)) or [CP2Fe2(mu-SEt)(2)(4,4'-CNC6H4OC6H4NC)(2)] (BF4)(2) (2b(BR4)(2)), respectively. The new-type 24-membered ring tetranuclear iron-thiolate-aryldiisocyanide metallocyclophane complex [Cp4Fe4(mu-SEt)(4)(mu-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(isocyanomethypbenzene 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(mu-SEt)(4)(4,4'-CNC6H4OC6H4NP2][BF4](4) (3b(BF4)(4)). The spectroscopic and electrochemical properties of four iron-sulfur core complexes were determined.

• 出版日期2017-1
• 单位中山大学