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Alkaline-Earth Metal Alkylaluminate Chemistry Revisited

机译:再谈碱土金属烷基铝酸盐化学

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摘要

Heterobimetallic peralkylated calcium complexes [Ca(AlR4)(2)](n) (R = Me, Et) were obtained from {Ca[N(SiMe3)(2)](2)}(2) and an excess AlR3 in almost quantitative yield. A similar silylamide elimination protocol was previously applied for the synthesis of the corresponding ytterbium and samarium complexes, The solid-state structure of polymeric [Ca(AlEt4)(2)](n) revealed agostically linked right-handed helices featuring a pitch of similar to 14 angstrom and a repeat length of similar to 27 angstrom with the latter composed of nine alkyl-bridged [Ca(AlEt4)(3)](-) and [Ca(AlEt4)](+) building units. Reaction of [Ca(AlR4)(2)](n) (R = Me, Et) with equimolar amounts of donor molecules gave X-ray structurally authenticated hexacoordinate monomeric adducts Ca(AlMe4)(2)Phen (Phen = 1,10-phenanthroline) and Ca-(AlEt4)(2)(thf)(2). Treatment of [Ca(AlEt4)(2)](n), [Yb(AlEt4)(2)](n), and Mg(AlMe4)(2) with excess thf resulted in the formation of solvent-separated ion pairs of composition [M(II)(thf)(6)][AlR4](2). Heating barely soluble [Ca(AlMe4)(2)](n) in a pressure tube produced vinyloxide-bridged complex [Ca(mu-OCH=CH2)-(thf)(4)}(2)][AlMe4](2) via thf degradation. Furthermore, treatment of MgMe2 with thf yielded quantitatively the donor adduct [Mg(Me(mu-Me)(thf)](2).
机译:异双金属过烷基化钙络合物[Ca(AlR4)(2)](n)(R = Me,Et)是从{Ca [N(SiMe3)(2)](2)}(2)和过量的AlR3中获得的。定量产量。先前已将类似的甲硅烷基酰胺消除方案用于相应的和sa络合物的合成。聚合物[Ca(AlEt4)(2)](n)的固态结构揭示了以前连接的右旋螺旋,其螺距相似到14埃,重复长度类似于27埃,后者由九个烷基桥接的[Ca(AlEt4)(3)](-)和[Ca(AlEt4)](+)建筑单元组成。 [Ca(AlR4)(2)](n)(R = Me,Et)与等摩尔量的供体分子反应,得到X射线结构鉴定的六配位单体加合物Ca(AlMe4)(2)Phen(Phen = 1,10 -菲咯啉)和Ca-(AlEt4)(2)(thf)(2)。用过量的thf处理[Ca(AlEt4)(2)](n),[Yb(AlEt4)(2)](n)和Mg(AlMe4)(2)导致溶剂分离的离子对的形成组成[M(II)(thf)(6)] [AlR4](2)。在压力管中加热几乎不溶的[Ca(AlMe4)(2)](n)生成环氧乙烷桥连的复合物[Ca(mu-OCH = CH2)-(thf)(4)}(2)] [AlMe4](2 )通过降解。此外,用thf处理MgMe2定量产生了供体加合物[Mg(Me(mu-Me)(thf)](2)。

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