Oxidative Addition and Reductive Elimination.ppt

Oxidative addition, reductive elimination Oxidative Addition and Reductive Elimination Oxidative Addition Basic reaction: The new M-X and M-Y bonds are formed using: the electron pair of the X-Y bond one metal-centered lone pair The metal goes up in oxidation state (+2) X-Y formally gets reduced to X-, Y- Common for transition metals, rare for main-group metals One reaction, multiple mechanisms Concerted addition, mostly with non-polar X-Y bonds H2, silanes, alkanes, O2, ... Arene C-H bonds more reactive than alkane C-H bonds (!) Intermediate A is a s-complex. Reaction may stop here if metal-centered lone pairsare not readily available. Final product expected to have cis X,Y groups. Concerted addition, arrested Cr(CO)5: coordinatively unsaturated, but metal-centered lone pairs not very available:s-complex One reaction, multiple mechanisms Stepwise addition, with polar X-Y bonds HX, R3SnX, acyl and allyl halides, ... low-valent, electron-rich metal fragment (IrI, Pd(0), ...) Metal initially acts as nucleophile. Coordinative unsaturation less important. Ionic intermediate (B). Final geometry (cis or trans) not easy to predict. One reaction, multiple mechanisms Radical addition has been observed but is relatively rare Tests: Formation R-R CIDNP Radical clocks: One reaction, many applications Oxidative addition is a key step inmany transition-metal catalyzed reactions Main exception: olefin polymerization The easy of addition (or elimination) can be tuned by the electronic and steric properties of the ancillary ligands The most common applications involve: a) Late transition metals (platinum metals) b) C-X, H-H or Si-H bonds Many are not too sensitive to O2 and H2Oand are now routinely used in organic synthesis. The Heck reaction Pd often added in the form of Pd2(dba)3. Usually with phosphine ligands. Typical catalyst loading: 1-5%. But there are examples with turnovers of 106 or more Heterogenous Pd precursors can also be used But the reac