Stepwise construction of a 4-hydroxyphenyl functionalized O,N,N-tridentate ferrocene-containing enaminone: Spectral, analytical and structural studies

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• 作者：Salvador Celedon ; Mauricio Fuentealba ; Thierry Roisnel ; Jean-Ren¨¦ Hamon ; David Carrillo ; Carolina Manzur
• 关键词：Ferrocene ; Enaminone ; Metalloligand ; Tridentate ligand ; O ; N ; N ligand ; X-ray structure
• 刊名：Inorganica Chimica Acta
• 出版年：2012
• 出版时间：15 July, 2012
• 年：2012
• 卷：390
• 期：Complete
• 页码：184-189
• 全文大小：433 K

文摘

Tetrahydropyranylation of methyl-4-hydroxybenzoate proceeds with formation of its corresponding THP aromatic ether THP-O-p-C₆H₄CO₂CH₃ (1; THP = tetrahydropyranyl, C₅H₉O). Reaction with in situ generated carbanion of acetylferrocene gave the protected organometallic complex Fc-C(O)CHC(OH)(p-C₆H₄-O-THP) (2, Fc(¦Ç⁵-C₅H₅)Fe(¦Ç⁵-C₅H₄)) featuring keto-enol functionality; subsequent acidic treatment of 2 afforded the 4-hydroxyphenyl substituted counterpart Fc-C(O)CHC(OH)(p-C₆H₄OH) (3) that exists as a 73/27 mixture of keto-enol/¦Â-diketone tautomers in DMSO solution. The functionalized tridentate metalloligand Fc-C(O)CHC(p-C₆H₄OH)N(H)CH₂CH₂NH₂ (4) incorporating O,N,N-donors is readily obtained upon Schiff base condensation of 3 with 1,2-diaminoethane. Complex 4 exists exclusively as its ferrocenyl-enaminone tautomer in solution and in the solid state. Compounds 1-4 were characterized by NMR (¹H, ¹³C) and IR spectroscopy as well as by elemental analysis and single-crystal X-ray diffraction.