金属有机化合物的基元反应.pptxVIP

金属有机化合物的基元反应一般有四类基元反应1 配体的配位和解离反应2 氧化加成反应和还原消除反应3 插入反应和消除反应（反插入反应）4 和金属络合的配体被进攻的反应第一页，共二十三页。插入反应与反插入反应插入反应为不饱和键插入到M-H,M-C之间的反应。它主要有两种类型：1 AB分子插入后分别与金属和R基团相连。2 AB分子插入后A同时与金属和R基团相连第二页，共二十三页。Definitions; Migratory Insertion - MIA=B is often COA=B is often an alkeneNumbering describes which atoms of the inserted ligand are bonded to M and X after the insertionOpposite of insertion is elimination (or “deinsertion” in USA)第三页，共二十三页。Definitions; Elimination - EThis is the same as the last slide with arrows going backwardsNamed by which atom contains the migrating groupUnfortunately the term “1,1-elimination” etc. is rarely used, even though it’s the opposite of a 1,1-insertion! 第四页，共二十三页。1,1-Migratory Insertion and a-Elimination Stereochemistry at carbonConfiguration at a stereogenic carbon is retainedSame applies to the reverse, i.e. a-elimination第五页，共二十三页。CO的插入反应: 由于CO和金属配位，金属的d电子向CO的反键轨道反馈，导致M-R键的削弱，同时CO中的碳-氧键也被削弱。插入反应这一过程有两种可能的途径1 CO 插入到M-R键中2 与金属相连的R基团迁移到CO上第六页，共二十三页。1,1-Migratory Insertion and a-Elimination Mechanistic questions The above reaction has been studied in detail, and much is known about the mechanism 第七页，共二十三页。研究表明是按R基团迁移的的途径进行的R基团迁移不可能得到4，研究表明产物1：2：3的比率为1：2：1，而且没有4 生成。第八页，共二十三页。1,1-Migratory Insertion and a-Elimination Where does the CO come from? CO that is inserted into Mn-Me bond is “unlabelled”, so it must have come from within the complex (i.e. mechanism is intramolecular)The 13CO in the product has remained cis to acyl and has not moved at all to the trans site. In other words, the reaction is under kinetic control (I.e. the first-formed product is observed).第九页，共二十三页。1,1-Migratory Insertion and a-Elimination Is this a cis process? The 13C labelled acyl product was synthesised by an alternative route shown above, and was then heated to promote eliminationOnly the cis isomer was observed, therefore in the reverse reaction (the 1,1-MI) the methyl group must be reacting with a CO that is cis to it.This logic relies on the Principle of Microscopic R