Reactivity of Bis(2,2,5,5-tetramethyl-2,5-disila-1-azacyclopent-1-yl)tin with CO2, OCS, and CS2 and Comparison to That of Bis[bis(trimethylsilyl)amido]tin

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• 作者：Constantine A. Stewart ; Diane A. Dickie ; Marie V. Parkes ; Josephat A. Saria ; Richard A. Kemp
• 刊名：Inorganic Chemistry
• 出版年：2010
• 出版时间：December 6, 2010
• 年：2010
• 卷：49
• 期：23
• 页码：11133-11141
• 全文大小：962K
• 年卷期：v.49,no.23(December 6, 2010)
• ISSN：1520-510X

文摘

The heterocumulenes carbon dioxide (CO₂), carbonyl sulfide (OCS), and carbon disulfide (CS₂) were treated with bis(2,2,5,5-tetramethyl-2,5-disila-1-azacyclopent-1-yl)tin {[(CH₂)Me₂Si]₂N}₂Sn, an analogue of the well-studied bis[bis(trimethylsilyl)amido]tin species [(Me₃Si)₂N]₂Sn, to yield an unexpectedly diverse product slate. Reaction of {[(CH₂)Me₂Si]₂N}₂Sn with CO₂ resulted in the formation of 2,2,5,5-tetramethyl-2,5-disila-1-oxacyclopentane, along with Sn₄(μ₄-O){μ₂-O₂CN[SiMe₂(CH₂)₂]}₄(μ₂-N═C═O)₂ as the primary organometallic Sn-containing product. The reaction of {[(CH₂)Me₂Si]₂N}₂Sn with CS₂ led to formal reduction of CS₂ to [CS₂]²⁻, yielding [{[(CH₂)Me₂Si]₂N}₂Sn]₂CS₂{[(CH₂)Me₂Si]₂N}₂Sn, in which the [CS₂]²⁻ is coordinated through C and S to two tin centers. The product [{[(CH₂)Me₂Si]₂N}₂Sn]₂CS₂{[(CH₂)Me₂Si]₂N}₂Sn also contains a novel 4-membered Sn−Sn−C−S ring, and exhibits a further bonding interaction through sulfur to a third Sn atom. Reaction of OCS with {[(CH₂)Me₂Si]₂N}₂Sn resulted in an insoluble polymeric material. In a comparison reaction, [(Me₃Si)₂N]₂Sn was treated with OCS to yield Sn₄(μ₄-O)(μ₂-OSiMe₃)₅(η¹-N═C═S). A combination of NMR and IR spectroscopy, mass spectrometry, and single crystal X-ray diffraction were used to characterize the products of each reaction. The oxygen atoms in the final products come from the facile cleavage of either CO₂ or OCS, depending on the reacting carbon dichalogenide.