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单击此处编辑母版标题样式,单击此处编辑母版文本样式,第二级,第三级,第四级,第五级,*,Chapter 7,Electrophilic,and,Nucleophilic,Addition and Abstraction,Outline,A.,Introduction,B.,Nucleophilic addition to CO and CNR,C.,Nucleophilic addition to olefins and acetylenes,D.,Nucleophilic abstraction,E.,Electrophilic,addition,F.,Electrophilic,abstraction,1.,The Organometallic Chemistry of the Transition Metals,Robert H. Crabtree, 3rd Edition,2001,Chapter 8.,2.,Organotransition,Metal Chemistry,Akio Yamamoto,1986,. 272-286,References,A. Introduction,Possible outcomes for the reactions with nucleophiles,Possible outcomes for reactions with,electrophiles,There are two possible outcomes for the reactions with,nucleophiles:,Nucleophilic addition,- reagent stays on metallic fragment,e.g.,Nucleophilic abstraction,- reagents do not stay with,metallic fragment,e.g.,There are also two possible outcomes for reactions,with electrophiles:,(1),Electrophilic,addition,- reagent stays with metallic fragment.,(Me,3,OBF,4,is used to supply Me,+,.),(2),Electrophilic,abstraction,- reagent does not stay with metal.,e.g.,In general:,B. Nucleophilic addition to CO and related ligands,Review questions,Q1.,Consider the reactions below, which one would you,expect to be faster?,Q2.,Provide the product of the following reactions,Nucleophilic addition to coordinated,olefins and acetylenes,Most common features,:,*,Attack from the opposite side of M,*,Regio,chemistry ?,e.g.,attack site 1 or 2 ?,Attacked site: 2,1,1,Exercises.,Give the products of the following reactions.,Site of selectivity.,If there are more than one type of olefins bonded to a metal, which one will be attacked?,e.g.,There are several rules:,Rule 1.,Polyenes,reacts before,polyenyls,polyenes,(even # C),polyenyls,(odd # C),(Davies-Green-,Mingos,Rules,),Rule 2. Open ligand reacts before closed ligands,open ligand closed ligand,cyclopropenyl,Rule 3. Usually terminal addition,Exercises.,Give the products of the following reactions.,first even,D. Nucleophilic abstractions.,There are a few special cases where nucleophilic abstraction can occur.,(1) Abstraction of acidic protons.,E.,Electrophilic,addition,Electrophilic,addition to metals.,(Special oxidative addition reaction),(2),Electrophilic,addition to ligands.,Electrophilic,addition to metals.,(Special oxidative addition reaction),e.g.,(2),Electrophilic,addition to ligands.,-,-,-,(,),Exercises.,Give the products of the following reactions.,The initially formed complex may undergo further,transformation.,e.g.,18e,16e or 18e ?,F.,Electrophilic,abstraction,Some groups can be,electrophilically,abstracted,e.g.,
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