教案2-1-主族课件.pptVIP

2021/10/15 * 自体显示剂,如4?(hydroxymethyl)biphenyl，可用于RLi的直接滴定: 如果在溶液中RLi的浓度0.1M,则可以通过1H?NMR谱使用内标法(?1.0?RCH2Li?1.3ppm)来进行测定。 2021/10/15 * 锂化合物结构特征:在溶液和固态中都会倾向形成多聚物单元(oligomeric units)。最典型的例子就是固态甲基锂。结构分析表明它是由(CH3Li)4单元按照立方体心方式堆积而成;(CH3Li)4可以看成是由4个CH3加冠于Li4四面体的4个面而组成。 2021/10/15 * 从Li?C的间距可以看到(LiCH3)4中的甲基与相邻的Li4四面体中的Li之间存在着相互作用;这些分子间作用力导致了(CH3Li)4的低挥发性,以及在无溶剂化作用介质中的不溶性。 叔丁基锂的结构与甲基锂的结构相似，但分子间作用力较弱。因此与MeLi不同，t?BuLi可溶于非极性溶剂中，并且在70?C/1mbar的条件下升华。 2021/10/15 * 有机锂化合物的缔合度 2021/10/15 * 在独立的(CH3Li)4分子中,轴向的Li(sp3)杂化轨道为空轨道，在晶体中它与相邻的(CH3Li)4上的甲基相互作用;在溶液中可以接受配体的配位(Lewis碱，溶剂分子)。如(?C6H5LiOEt2)；在螯合配体TMEDA存在下，则可得到二聚结构的晶体。  2021/10/15 * 给出一个主族金属化合物应用的实例或文献。并加以评论。 2021/10/15 * 2021/10/15 * Group 1 - Alkali metals Group 2 - Alkaline earth metals Much of the important chemistry of the alkali and alkaline earth metals can be understood on the basis of their low ionization enthalpies (or electronegativities) and the favourability of ionic bonding. 2021/10/15 * Reactions of the elements with water: Group 1: M(s) + H2O(l) ? M+(aq) + (OH)-(aq) + ? H2(g) Group 2: M(s) + 2 H2O(l) ? M+2(aq) + 2 (OH)-(aq) + H2(g) These reactions are very exothermic and increase in violence from the lightest to the heaviest elements in the group (enough to ignite the H2 for the heavier elements). The non-reversible nature of this reaction means that such metals are very useful for drying many kinds of solvents. Group 1 - Alkali metals Group 2 - Alkaline earth metals The s-block metals are used as reducing agents for an immense number of different types of compounds. More generally: Group 1: M(s) + HOR ? M+ + (OR)- + ? H2(g) Group 2: M(s) + 2 HOR ? M+2 + 2 (OR)- + H2(g) These reactions make metal alkoxides that are very useful for the synthesis of other products using metathesis reactions. Metathesis indicates that the reagents exchange ligands with one another. Such reactions are especially favourable when it produces a metal halide because of the large exothermicity provided by the lattice