title: Reaction mechanism of palladium-catalyzed silastannation of allenes by density functional theory.
abstract: The reaction mechanism of Pd(0)-catalyzed allenes silastannation reaction is investigated by the density functional method B3LYP. The overall reaction mechanism is examined. For the allene insertion step, the Pd-Si bond is preferred over the Pd-Sn bond. The electronic mechanism of the allene insertion into Pd-Si bond to form sigma-vinylpalladium (terminal-insertion) and sigma-allylpalladium (internal-insertion) insertion products is discussed in terms of the electron donation and back-donation. It is found that the electron back-donation is significant for both terminal- and internal-insertion. During allene insertion into Pd-Si bond, internal-insertion is preferred over terminal-insertion. By using methylallene, the regio-selectivity for the monosubstituted allene insertion into Pd-Si and Pd-Sn bond is analyzed.
authors.affiliation: State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, People's Republic of China.
authors.forename: Meiyan
authors.initials: M
authors.lastname: Wang
authors.forename: Lin
authors.initials: L
authors.lastname: Cheng
authors.forename: Bo
authors.initials: B
authors.lastname: Hong
authors.forename: Zhijian
authors.initials: Z
authors.lastname: Wu
mesh_terms: D000466:Alkadienes / Q000737:chemistry*; D002384:Catalysis; D003198:Computer Simulation; D008956:Models, Chemical; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry; D010165:Palladium / Q000737:chemistry*; D012825:Silicon / Q000737:chemistry*; D014001:Tin / Q000737:chemistry*
chemical_list: D000466:Alkadienes; D009942:Organometallic Compounds; D010165:Palladium; D014001:Tin; D012825:Silicon