Iron(III) Half-Sandwich Complexes of the Two-Legged Piano-Stool [CpFe(aryl)Cl] Type from the Corresponding Aryliron(II) Precursors

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• 作者：Heiko Bauer ; Mark W. Wallasch ; Gotthelf Wolmershä ; user ; Yu Sun and Helmut Sitzmann
• 刊名：European Journal of Inorganic Chemistry
• 出版年：2017
• 出版时间：January 10, 2017
• 年：2017
• 卷：2017
• 期：2
• 页码：505-510
• 全文大小：1320K
• ISSN：1099-0682c

文摘

Instead of reacting with the σ-mesityliron(II) complex [Cp′′′Fe(σ-C₆H₂Me₃-2,4,6)] (1; Cp′′′ = 1,2,4-tri-tert-butylcyclopentadienyl) to form a cyclohexadienyl(cyclopentadienyl)iron(II) sandwich complex with palladium coordination to the ipso carbon atom of the six-membered ring, palladium(II) chloride oxidized 1 to the mesityliron(III) complex [Cp′′′Fe(σ-C₆H₂Me₃-2,4,6)Cl] (5) with a two-legged piano-stool geometry. The oxidation of [⁴CpFe(σ-C₆H₂Me₃-2,4,6)] (4; ⁴Cp = tetraisopropylcyclopentadienyl) to [⁴CpFe(σ-C₆H₂Me₃-2,4,6)Cl] (6) was accomplished with hexachloroethane. Two other derivatives, [⁴CpFe(σ-C₆H₃iPr₂-2,6)Cl] (7) and [⁵CpFe(σ-C₆H₃iPr₂-2,6)Cl] (8; ⁵Cp = pentaisopropylcyclopentadienyl), could also be obtained by the same method. The molecular structures of 5 and 6 are compared with the structure of the (tetraisopropylcyclopentadienyl)iron(III) dibromide [⁴CpFeBr₂] (9), which was formed from the iron(II) analogue [⁴CpFe(µ-Br)]₂ during attempted nucleophilic substitution with an arylmagnesium bromide.