Diametrically opposite trends in alkene insertion in late and early transition metal compounds: relevance to transition-metal-catalyzed polymerization of polar vinyl monomers.
Variable-temperature 1H NMR studies of the reaction of cationic (alpha-diimine)Pd-alkyl complexes with alkenes are presented. The studies reveal that vinyl bromide coordinates to the Pd(II)-Me complex followed by migratory insertion and beta-bromo elimination, to generate free propene. Propene further reacts to give beta-agostic Pd(II)-tert-butyl species. From the reactions with vinyl bromide, stable chloro-bridged dicationic Pd complex was isolated and characterized. For a series of alkenes (CH2=CHX), the rate for migratory insertion decreases as follows: X = CO2Me > Br > H > Me.
Kang
Myeongsoon
M
Department of Chemistry, The Pennsylvania State University, University Park, Pennsylvania 16802, USA.
Sen
Ayusman
A
Zakharov
Lev
L
Rheingold
Arnold L
AL