Abstract
The gas-phase hydroaminoalkylation reaction of propene catalyzed by group 4 (M = Ti, Zr and Hf) metal amido complexes [(≡Si–O-)(M(-NMe2)3] was investigated by using PBE0-D3/SVP//TZVP level of theory. The geometrical analysis traced the formation of the metallaaziridines and the azametallacyclopentanes as key intermediates in these reactions. The metallaaziridines were simulated through the activation of α-C-H bonds of the amido groups; while the azametallacyclopentanes were configured by slotting the propene double bond onto the M − C bonds of the metallaaziridines. The latter reaction was considered the rate-determining step. Thermochemical calculations showed that the order of catalytic activity is: Ti ≥ Zr > Hf; while the preference of the azametallacyclopentanes is: Hf > Zr ≥ Ti.
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•Hydroaminoalkylation reaction of propene catalyzed by metals of group 4 is investigated.•The formation of the metallaaziridines and the azametallacyclopentanes are the key intermediates in these reactions.•Thermochemical calculations showed that the order of catalytic activity is: Ti ≥ Zr > Hf; while the preference of the azametallacyclopentanes formation is: Hf > Zr ≥ Ti.