Side chain functionalized η⁵-tetramethyl cyclopentadienyl complexes of Rh and Ir with a pendant primary amine group

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• 作者：Thomas Reiner ; Dominik Jantke ; Andreas Raba ; Alex ; er N. Marziale ; Jö ; rg Eppinger
• 关键词：Rhodium ; Iridium ; Cyclopentadiene derivative ; Functionalized metal complexes ; Metal peptide conjugation
• 刊名：Journal of Organometallic Chemistry
• 出版年：2009
• 出版时间：15 May 2009
• 年：2009
• 卷：694
• 期：12
• 页码：1934-1937
• 全文大小：263 K

文摘

Conversion of 2-(2,3,4,5-tetramethylcyclopentadien)ethylamine tautomere C₅Me₄H₂(CHCH₂)NH₂ (1) with MCl₃ · n H₂O (M = Rh, Ir) under acidic conditions gives the respective μ-chloro-bridged chelates [(η⁵-Me₄Cp(CH₂)₂NH₃)RhCl₂]₂Cl₂ (2) and [(η⁵-Me₄Cp(CH₂)₂NH₃)IrCl₂]₂Cl₂ (3). The dimeric complexes are received as ammonium salts and thus display good solubility in strong donor solvents such as water and DMSO. Addition of triphenyl phosphine converts Rh-dimer 2 into the mononuclear phosphine complex 4. Under basic conditions, no intramolecular coordination of the pendant NH₂ is observed and thus the primary amino group of 4 reacts selectively with succinic anhydride by formation of a peptide bond. Hence, the electrophilic metal center and the latent nucleophilic nitrogen, which represent complementary functionalities, can be addressed separately under the appropriate reaction conditions.