Preparation, Characterization, and Reactivity of (3-Methylpentadienyl)iron(1+) Cations

详细信息    查看全文

• 作者：Subhabrata Chaudhury ; Shukun Li ; Dennis W. Bennett ; Tasneem Siddiquee ; Daniel T. Haworth ; William A. Donaldson
• 刊名：Organometallics
• 出版年：2007
• 出版时间：October 22, 2007
• 年：2007
• 卷：26
• 期：22
• 页码：5295 - 5303
• 全文大小：219K
• 年卷期：v.26,no.22(October 22, 2007)
• ISSN：1520-6041

文摘

The title cations (9 and 12) were prepared by dehydration of (3-methyl-2,4-pentadien-1-ol)Fe(CO)₂L⁺complexes. The structure of the (CO)₂PPh₃-ligated 12 was determined by single-crystal X-ray analysis.Reaction of carbon and heteroatom nucleophiles to (3-methylpentadienyl)Fe(CO)₃⁺ cations 9 and 12proceeds either via attack at the dienyl terminus to give (3-methyl-1,3Z-diene)iron complexes or viaattack at the internal carbon, followed by carbon monoxide insertion and reductive elimination to afford3-methyl-4-substituted cyclohexenones. Cyclohexenone formation was found to be prevalent for additionof stabilized nucleophiles with strongly dissociated counterions to cation 9 (L = CO). Reaction of cation9 with sodium bis[(-)-8-phenylmenthyl] malonate gave a single diastereomeric cyclohexenone.