关键词:
transition metals
hydride and methyl derivatives
direct and transfer epimetallation
alkylidenes in C-C bond formation
Ziegler-Natta and ROMP catalysts
摘要:
A broad survey of both the simple and double decomposition modes of transition metal alkyls has been undertaken. From the two main processes of C-M bond rupture, homolysis, and beta-metal hydride elimination, the following modes of decomposition and types of useful reagents generated can be distinguished: 1) reductive decomposition of RnMEm-n to yield subvalent, carbene- or free-radical-like MEm-n, which can cleave pi- or (sigma-bonds by direct epimetallation;2) beta-metal hydride elimination to produce hydrometallating agents;3) combined reductive and beta-metal hydride eliminations to produce anionic, and hence more nucleophilic, epimetallating agents;4) alpha-metal hydride elimination thought to be involved in the transition state leading to C-C bond coupling from (RR'HC)(2)ME2 derivatives;5) alpha,mu-elimination from lithiated RHC(Li)-MEn-1, which produces alkylidenes, RHC = MEn-2, capable of ROMP catalysis;6) metal-hydrogen metathesis, whereby sufficiently acidic C-H bonds become C-M bonds;7) metal-metal metathesis, whereby RR'ME2 undergoes an equilibrating redistribution reaction to form R2ME2 and R'2ME2;8) transfer epimetallation, in which epimetallation (point 1) is achieved with R2ME2 in one step by transfer of ME2 to the substrate with the concomitant loss of R groups;and 9) transfer epimetallation of olefins by R2TiE2 in hydrocarbons to produce titana(IV)cyclopropanes, which serve as active sites in Ziegler-Natta polymerization. In each situation, the reaction-mechanistic features are analyzed in terms of existing experimental data and evidence.