Reactions of alkali metal and yttrium alkyls with a sterically demanding bis(aryloxysilyl)methane: Formation of aryloxide complexes by Si-O bond cleavage
Reactions of alkali metal and yttrium alkyls with a sterically demanding bis(aryloxysilyl)methane: Formation of aryloxide complexes by Si-O bond cleavage
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碱金属和烷基钇与空间要求高的双（芳氧基甲硅烷基）甲烷的反应：通过 Si-O 键断裂形成芳氧基络合物
DOI：
10.1016/j.crci.2010.01.017
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发表时间：
2010
影响因子：
1.6
通讯作者：
Cornish A
中科院分区：
文献类型：
--
作者：
Cornish A
在辅助碱net3的存在下，双（溴基甲基硅基）甲烷（BrSiMe2）2CH2(1)与两个等量的2,6-二异丙基苯酚（Ar 'OH）反应，得到双（芳基氧基硅基）甲烷（Ar 'OSiMe2）2CH2(2)，作为后续处理的无色油。在[K(OBut)]存在下，2与[Li(Bun)]的反应促进了Si-O键的裂解，该反应的唯一可分离产物是无色结晶的杂双金属配合物[{Li(OAr ')}2{K(OAr ')}2(THF)4](3)。2与一等量的[Li(Bun)]在一等量的[K(o)]存在下进行原位反应，随后加入一等量的[Y(I)3(THF)3.5]，得到无色结晶的[Y(OAr ')(I)2(THF)3](4)作为唯一可分离的产物。在室温下，[Y(Bn)3(THF)3] （Bn=CH2C6H5）与1等量的2在甲苯中未发生反应；加热溶液导致分解和回收2。在THF中，2和一个等价物[Y(Bn)3(THF)3]之间的反应导致Si-O键断裂，同时形成Si-C键，得到（BnSiMe2）2CH2(5)作为无色油和无色结晶化合物[Y(OAr ')2(Bn)(THF)](7)和[Y(OAr ')3(THF)2](8)，它们通过分数结晶分离。为了尝试用合理的路线制备7，由[Y(I)3(THF)3.5]与[K(OAr ')]的两个当量反应制备[Y(OAr ')2(I)(THF)2](6)。然而，虽然6可以通过合理的除盐路线制备，但试图将其转化为7却导致8被回收为唯一可分离的产物。这被认为是schlenk型平衡的结果，这得到了纯6在苯中溶解导致12h 1h NMR谱中额外存在8的观察的支持。化合物7由[Y(Bn)3(THF)3]与两种HOAr '的等价物反应合理制备。然而，尽管可以分离出足够数量的晶体7用于分析，但核磁共振光谱与溶液中从schlenk型平衡形成的8相一致。化合物2-8已通过x射线衍射、核磁共振和红外光谱以及CHN微量分析进行了不同的表征。
Reaction of bis(bromodimethylsilyl)methane (BrSiMe2)2CH2(1) with two equivalents of 2,6-diisopropylphenol (Ar′OH) in the presence of the auxiliary base NEt3affords the bis(aryloxysilyl)methane (Ar′OSiMe2)2CH2(2) as a colourless oil following work-up. The reaction of 2 with [Li(Bun)] in the presence of [K(OBut)] promoted Si-O bond cleavage and the sole isolable product from this reaction was found to be the colourless, crystalline heterobimetallic complex [{Li(OAr′)}2{K(OAr′)}2(THF)4] (3). The in situ reaction of 2 with one equivalent of [Li(Bun)] in the presence of one equivalent of [K(OBut)] and subsequent addition to one equivalent of [Y(I)3(THF)3.5] afforded colourless, crystalline [Y(OAr′)(I)2(THF)3] (4) as the only isolable product. No reaction was observed between [Y(Bn)3(THF)3] (Bn=CH2C6H5) and one equivalent of 2 in toluene at room temperature; heating solutions led to decomposition and recovery of 2. In THF, the reaction between 2 and one equivalent of [Y(Bn)3(THF)3] resulted in Si-O bond cleavage with concomitant Si-C bond formation to give (BnSiMe2)2CH2(5) as a colourless oil and the colourless, crystalline compounds [Y(OAr′)2(Bn)(THF)] (7), and [Y(OAr′)3(THF)2] (8) which were separated by fractional crystallisation. In an attempt to prepare 7 by a rational route, [Y(OAr′)2(I)(THF)2] (6) was prepared from the reaction of [Y(I)3(THF)3.5] with two equivalents of [K(OAr′)]. However, although 6 could be prepared by a rational salt elimination route, attempts to convert it to 7 resulted instead in 8 being recovered as the only isolable product. This is proposed to be the result of Schlenk-type equilibria, which is supported by the observation that dissolution of pure 6 in benzene results in the additional presence of 8 in the1H NMR spectrum over 12h. Compound 7 was prepared rationally from the reaction between [Y(Bn)3(THF)3] and two equivalents of HOAr′. However, although crystalline 7 could be isolated in sufficient quantities for analysis, NMR spectra were consistent with the formation of 8 in solution from Schlenk-type equilibria. Compounds 2–8 have been variously characterised by X-ray diffraction, NMR and FTIR spectroscopy, and CHN microanalyses.
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