Synthesis and Thermal Rearrangement of 1,2-Di(p-tolyl)-1,2-dimethyldisilanylene Bridged Bis(cyclopentadienyl)tetracarbonyldiiron

Abstract

Abstract: Cl₂MeSiSiMeCl₂(1) reacted with C₅H₅Li and subsequently with p-tolylmagnesium bromide to afford C₅H₅(p-Tol)MeSiSiMe(p-Tol)C₅H₅(2). The latter further reacted with Fe(CO)₅ gave the title complex [η⁵, η⁵-C₅H₄(p-Tol)MeSiSiMe(p-Tol)C₅H₄]Fe₂(CO)₂(μ-CO)₂(3). Meanwhile, two mono-silicon bridged by-products [η⁵, η⁵-(p-Tol)₂MeSiSiMe(C₅H₄)₂]Fe₂(CO)₂(μ-CO)₂(4) and [η⁵, η⁵-(p-Tol)Me₂SiSiMe(C₅H₄)₂]Fe₂(CO)₂(μ-CO)₂(5) were also obtained. Product 3 contains predominantly the cis isomer(3a), which was isolated inpure form by simple recrystallization. Compound 3a underwent the metathesis rearrangement reaction between Si—Si and Fe—Fe bonds under thermal conditions giving complex [η⁵-(p-Tol)MeSiC₅H₄Fe(CO)₂]₂(6). This product was a mixture of cis and trans isomers with a molar ratio about 4:3, demonstrating that the reaction does not involve a concerted process. The molecular structure of compound 4 was determined by X-ray diffraction method.

Key words: Thermal rearrangement, Silicon-silicon bond, Cyclopentadienyl, Metathesis

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SUN Huai-Lin, ZHANG Hui-Li, MA Yu-Xi
. Synthesis and Thermal Rearrangement of 1,2-Di(p-tolyl)-1,2-dimethyldisilanylene Bridged Bis(cyclopentadienyl)tetracarbonyldiiron[J]. Chem. J. Chinese Universities, doi: .

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Synthesis and Thermal Rearrangement of 1,2-Di(p-tolyl)-1,2-dimethyldisilanylene Bridged Bis(cyclopentadienyl)tetracarbonyldiiron

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