Insertion Aptitudes and Insertion Regiochemistry of Various Alkenes Coordinated to Cationic (σ-R)(diimine)palladium(II) (R = −CH3, −C6H5). A Theoretical Study

The coordination of a range of substituted alkenes (C 2 H 3 X; X = H, CH 3, t-Bu, CN, CO 2 CH 3, CF 3, OCH 3, CHCH 2, C 6 H 5, F, Cl, Br) to a cationic methyl- or phenylpalladium(II)diimine complex and the subsequent migratory insertion into the methyl−palladium and phenyl−palladium bonds are studied using DFT calculations at the B3LYP level of theory. The focus of this investigation is on monitoring the insertion barrier and the regiochemical outcome as a function of alkene properties, with special attention to the functionalized alkene as a potential comonomer in polymerization. In general, electron-rich alkenes coordinate more strongly, whereas electron poor alkenes insert more readily. The barriers of insertion range from 4.7 to 26.5 kcal/mol, and mostly the 2,1-insertion is favored. In all cases the alkenes have a weaker coordination to the phenylpalladium(II)diimine compared to the methylpalladium(II)diimine complex and, as expected, a lower insertion barrier.