Mono-BHT heteroleptic magnesium complexes: synthesis, molecular structure and catalytic behavior in the ring-opening polymerization of cyclic esters

Ilya E. Nifant’ev, A. V. Shlyakhtin, Vladimir V. Bagrov, Mikhail E. Minyaev, Andrei V. Churakov, S. G. Karchevsky, Kirill P. Birin, Pavel V. Ivchenko

Dalton Transactions · 2017 · 62 citations · 72 references

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Abstract

with a series of σ-electron donors (Sub) have been estimated by DFT calculations. These results demonstrate that the substitution of THF by Sub in a dimeric molecule is an energetically allowed process, whereas the dissociation of dimers is energetically unfavorable. DFT modeling of ε-CL and (dl)-lactide ROP catalyzed by dimeric and monomeric complexes showed that a cooperative effect of two magnesium atoms occurs within the ROP for binuclear catalytic species. A comparison of the reaction profiles for ROP catalyzed by binuclear and mononuclear species allowed us to conclude that the binuclear mechanism is favorable in early stages of ROP initiated by dimers 3 and 5.

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