基元反应(插入)107.ppt

氧化加成和还原消除反应 a） b） 金属的氧化态及配位数均减少2； 配位饱和的高价金属变为配位不饱和的低价金属。 氧化加成反应的特点： A-B键发生断裂，同时加成到过渡金属上； 金属的氧化态及配位数均增加2； 配位不饱和的低价金属变为配位饱和的高价金属。 还原消除反应的特点： Reductive elimination is the reverse of oxidative addition and is usually the last step of many catalytic processes. It is exceptionally important for organic synthetic applications because it is the major way in which transition metals are used to make carbon-carbon and carbon-hydrogen bonds ! * 氧化加成和还原消除反应 a） b） 金属的氧化态及配位数均减少2； 配位饱和的高价金属变为配位不饱和的低价金属。 氧化加成反应的特点： A-B键发生断裂，同时加成到过渡金属上； 金属的氧化态及配位数均增加2； 配位不饱和的低价金属变为配位饱和的高价金属。 还原消除反应的特点： A = B为C = C、 R’RC = O、C = N等。 :A – B为一氧化碳:C O、异氰 :C N – R、卡宾:CR2等。 插入反应和消除（反插入）反应 插入反应是指不饱和键插入到M - H键或M - C键中。 特点：金属的氧化态及配位数均没有变化。 Oxidative addition/reductive elimination processes are central to a vast array of synthetically useful organometallic reactions (eg. “Heck” reaction), and occur because of the ability of transition metals to exist in several different oxidation states, in contrast to nontransition metal compounds, which usually have closed shell configurations. In fact, it is the facile shuttling between oxidation states that makes transition metals so useful in organic synthesis. 氧化加成和还原消除是以Vaska(1968)配合物IrCl(CO)(PPh3)2和Wilkinson配合物RhCl(PPh3)3的发现及反应性研究开始的，对了解催化反应机理非常重要。 Note that many of these result in the formation of M-H and M-C bonds, and in the “activation” of a range of organic substrates. Concerted oxidative additions are best known for nonpolar substrates, eg. H2, and C-H bonds. Oxidative addition via SN2-type processes is most often observed with strongly nucleophilic, low valent metals and classic SN2 substrates such as organic halides and tosylates. Collman’s reagent, Na2Fe(CO)4, a very potent nucleophile, reacts with RX via SN2. Competing radical chain mechanism for oxidative addition.Traces of air sometimes promote the reaction of complexes which normally require strict exclusion of air, and serves as a warning that the mechanism by which a reaction proceeds ma