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Issue 36, 2017
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Mono-BHT heteroleptic magnesium complexes: synthesis, molecular structure and catalytic behavior in the ring-opening polymerization of cyclic esters

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Abstract

Numerous heteroleptic 2,6-di-tert-butyl-4-methylphenolate (BHT) magnesium complexes have been synthesized by treatment of (BHT)MgBu(THF)2 with various alcohols. Molecular structures of the complexes have been determined by X-ray diffraction. The magnesium coordination number in [(BHT)Mg(μ-OBn)(THF)]2 (3) and [(BHT)Mg(μ-O-tert-BuC6H4)(THF)]2 (4) is equal to 4. Complexes formed from esters of glycolic and lactic acids, [(BHT)Mg(μ-OCH2COOEt)(THF)]2 (5) and [(BHT)Mg(μ-OCH(CH3)COOCH2COOtBu)(THF)]2 (6) contain chelate fragments with pentacoordinated magnesium. Compounds 3–6 contain THF molecules coordinated to magnesium atoms. Complex {(BHT)Mg[μ-O(CH2)3CON(CH3)2]}2 (7) does not demonstrate any tendency to form an adduct with THF. It has been experimentally determined that complexes 3 and 5 are highly active catalysts of lactide polymerization. The activity of 4 is rather low, and complex 7 demonstrates moderate productivity. According to DOSY NMR experiments, compounds 3 and 5 retain their dimeric structures even in THF. The free energies of model dimeric [(DBP)Mg(μ-OMe)(Sub)]2 and monomeric (DBP)Mg(OMe)(Sub)2 products on treatment of [(DBP)Mg(μ-OMe)(THF)]2 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.

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

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Publication details

The article was received on 07 Jul 2017, accepted on 28 Aug 2017 and first published on 29 Aug 2017


Article type: Paper
DOI: 10.1039/C7DT02469J
Citation: Dalton Trans., 2017,46, 12132-12146
  • Open access: Creative Commons BY-NC license
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    Mono-BHT heteroleptic magnesium complexes: synthesis, molecular structure and catalytic behavior in the ring-opening polymerization of cyclic esters

    I. E. Nifant'ev, A. V. Shlyakhtin, V. V. Bagrov, M. E. Minyaev, A. V. Churakov, S. G. Karchevsky, K. P. Birin and P. V. Ivchenko, Dalton Trans., 2017, 46, 12132
    DOI: 10.1039/C7DT02469J

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