Bowman Lyndsey J, Izod Keith, Clegg William, Harrington Ross W, Smith J David, Eaborn C
Department of Chemistry, School of Natural Sciences, Bedson Building, University of Newcastle, Newcastle upon Tyne, NE1 7RU, UK.
Dalton Trans. 2006 Jan 21(3):502-8. doi: 10.1039/b510692c. Epub 2005 Oct 26.
The oxygen-bridged, silicon-substituted alkane {(Me3Si)2CH(SiMe2)}2O (1) may be prepared by the reaction of {(Me3Si)2CH}Li with ClSiMe2OSiMe2Cl in refluxing THF. Similarly, the alkane {(Me3Si)(Me2MeOSi)CH(SiMe2CH2)}2 (2) is readily accessible from the reaction between {(Me3Si)(Me2MeOSi)CH}Li and ClSiMe2CH2CH2SiMe2Cl under the same conditions. Compound 1 reacts with two equivalents of MeK to give the polymeric complex [[{(Me3Si)2C(SiMe2)}2O]K2(OEt2)]infinity [5(OEt2)] after recrystallisation. Treatment of 2 with two equivalents of either MeLi or MeK gives the corresponding complexes [{(Me3Si)(Me2MeOSi)C(SiMe2CH2)}2Li][Li(DME)3] [7(DME)3] and [{(Me3Si)(Me2MeOSi)C(SiMe2CH2)}2K2]n (8), respectively, after recrystallisation. Treatment of the alkane (Me3Si)2(Me2MeOSi)CH with one equivalent of MeK gives the polymeric complex [{(Me3Si)2(Me2MeOSi)C}K]infinity (3). These compounds have been identified by 1H and 13C{1H} NMR spectroscopy and elemental analyses and compounds 5(OEt2), 7(DME)3 and 3 have been further characterised by X-ray crystallography. Compound 7(DME)3 crystallises as a solvent-separated ion pair, whereas 5(OEt2) and 3 adopt polymeric structures in the solid state.
氧桥连、硅取代的烷烃{(Me3Si)2CH(SiMe2)}2O (1)可通过{(Me3Si)2CH}Li与ClSiMe2OSiMe2Cl在回流四氢呋喃中反应制备。类似地,在相同条件下,通过{(Me3Si)(Me2MeOSi)CH}Li与ClSiMe2CH2CH2SiMe2Cl反应可轻松制得烷烃{(Me3Si)(Me2MeOSi)CH(SiMe2CH2)}2 (2)。化合物1与两当量的MeK反应,重结晶后得到聚合物配合物[[{(Me3Si)2C(SiMe2)}2O]K2(OEt2)]∞[5(OEt2)]。用两当量的MeLi或MeK处理2,重结晶后分别得到相应的配合物[{(Me3Si)(Me2MeOSi)C(SiMe2CH2)}2Li][Li(DME)3] [7(DME)3]和[{(Me3Si)(Me2MeOSi)C(SiMe2CH2)}2K2]n (8)。用一当量的MeK处理烷烃(Me3Si)2(Me2MeOSi)CH得到聚合物配合物[{(Me3Si)2(Me2MeOSi)C}K]∞(3)。这些化合物已通过1H和13C{1H}核磁共振光谱以及元素分析进行了鉴定,化合物5(OEt2)、7(DME)3和3已通过X射线晶体学进一步表征。化合物7(DME)3以溶剂分隔离子对的形式结晶,而5(OEt2)和3在固态时采用聚合物结构。