DFT calculations as a ligand toolbox for the synthesis of active initiators for ROP of cyclic esters

Jędrzkiewicz, Dawid; Kantorska, D.; Wojtaszak, J.; Ejfler, Jolanta; Szafert, Sławomir

doi:10.1039/c7dt00394c

Cited by 10 publications

(6 citation statements)

References 51 publications

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“…In conclusion, we should like to emphasize that some aspects of the molecular structure of ROP precatalysts have been refined by DFT modeling [148,152,153,154,155,156,157]. However, the results of such modeling do not reflect fully the catalytic behavior of these complexes and therefore were irrelevant for our review.…”

Section: Coordination Polymerization Of Lactides and Glycolidementioning

confidence: 99%

Coordination Ring-Opening Polymerization of Cyclic Esters: A Critical Overview of DFT Modeling and Visualization of the Reaction Mechanisms

Nifant’ev

Ivchenko

2019

Molecules

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Ring-opening polymerization (ROP) of cyclic esters (lactones, lactides, cyclic carbonates and phosphates) is an effective tool to synthesize biocompatible and biodegradable polymers. Metal complexes effectively catalyze ROP, a remarkable diversity of the ROP mechanisms prompted the use of density functional theory (DFT) methods for simulation and visualization of the ROP pathways. Optimization of the molecular structures of the key reaction intermediates and transition states has allowed to explain the values of catalytic activities and stereocontrol events. DFT computation data sets might be viewed as a sound basis for the design of novel ROP catalysts and cyclic substrates, for the creation of new types of homo- and copolymers with promising properties. In this review, we summarized the results of DFT modeling of coordination ROP of cyclic esters. The importance to understand the difference between initiation and propagation stages, to consider the possibility of polymer–catalyst coordination, to figure out the key transition states, and other aspects of DFT simulation and visualization of ROP have been also discussed in our review.

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Section: Coordination Polymerization Of Lactides and Glycolidementioning

confidence: 99%

Coordination Ring-Opening Polymerization of Cyclic Esters: A Critical Overview of DFT Modeling and Visualization of the Reaction Mechanisms

Nifant’ev

Ivchenko

2019

Molecules

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“…The idea for the rationalization of the synthesis of chiral homoleptic monomers was to carry out the ligand redistribution reaction while using strictly designed heterodimers . Combining the chiral ligands with the same amine arms but a different aryl core, S -(O-dtBu,N-mb)-H and R -(O-ptBu,N-mb)-H, in the necessary 1/1 stoichiometry, in the reaction with two equivalents of ZnEt 2 yielded crystals of the heterodimer ( R -(O-ptBu,N-mb))( S -(O-dtBu,N-mb))Zn 2 Et 2 (Figure ) with the aryl core substituents located in such a way that they influence the controlled decomposition of the dimer in toluene solution (Scheme ). This is the basis of the unique synthetic strategy that enabled monocrystals of (O-dtBu,N-mb) 2 Zn to be obtained (Figure ).…”

Section: Resultsmentioning

confidence: 99%

Serendipitous Synthesis Found in the Nuances of Homoleptic Zinc Complex Formation

2018

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A series of aminophenolate and aminonaphtholate homoleptic zinc complexes were obtained using a simple and unique synthetic strategy. A rigorous analysis of the byproduct supported modifications of the main course of the bis-chelation reaction. Controlled alcoholysis was followed by alternation and controlled anaerobic hydrolysis of ethyl-zinc aminophenolate or aminonaphtholate complexes. This new and intriguing reaction yielded a new class of zinc corona complexes. All the synthesized complexes were fully characterized in the solid state and in solution using X-ray and spectroscopic methods as well as density functional theory calculations.

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“…Metal alkoxy complexes are effective catalysts of ring-opening polymerization (ROP); the mechanistic paradigm for ROP initiated by metal alkoxides bases on “coordination-insertion” concept [13,14,15,16,17,18,19,20] (Scheme 1b). The density functional theory (DFT) modeling was successfully applied in the mechanistic study of coordination homopolymerization of lactones [21,22,23,24,25,26,27,28,29,30,31,32,33], lactides [31,34,35,36,37,38,39,40,41,42,43,44,45,46,47,48], cyclic carbonates [30,42,49,50] and phosphates [51].…”

Section: Introductionmentioning

confidence: 99%

DFT Visualization and Experimental Evidence of BHT-Mg-Catalyzed Copolymerization of Lactides, Lactones and Ethylene Phosphates

et al. 2019

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Catalytic ring-opening polymerization (ROP) of cyclic esters (lactides, lactones) and cyclic ethylene phosphates is an effective way to process materials with regulated hydrophilicity and controlled biodegradability. Random copolymers of cyclic monomers of different chemical nature are highly attractive due to their high variability of characteristics. Aryloxy-alkoxy complexes of non-toxic metals such as derivatives of 2,6-di-tert-butyl-4-methylphenoxy magnesium (BHT-Mg) complexes are effective coordination catalysts for homopolymerization of all types of traditional ROP monomers. In the present paper, we report the results of density functional theory (DFT) modeling of BHT-Mg-catalyzed copolymerization for lactone/lactide, lactone/ethylene phosphate and lactide/ethylene phosphate mixtures. ε-Caprolactone (ε-CL), l-lactide (l-LA) and methyl ethylene phosphate (MeOEP) were used as examples of monomers in DFT simulations by the Gaussian-09 program package with the B3PW91/DGTZVP basis set. Both binuclear and mononuclear reaction mechanistic concepts have been applied for the calculations of the reaction profiles. The results of calculations predict the possibility of the formation of random copolymers based on l-LA/MeOEP, and substantial hindrance of copolymerization for ε-CL/l-LA and ε-CL/MeOEP pairs. From the mechanistic point of view, the formation of highly stable five-membered chelate by the products of l-LA ring-opening and high donor properties of phosphates are the key factors that rule the reactions. The results of DFT modeling have been confirmed by copolymerization experiments.

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DFT calculations as a ligand toolbox for the synthesis of active initiators for ROP of cyclic esters

Cited by 10 publications

References 51 publications

Coordination Ring-Opening Polymerization of Cyclic Esters: A Critical Overview of DFT Modeling and Visualization of the Reaction Mechanisms

Coordination Ring-Opening Polymerization of Cyclic Esters: A Critical Overview of DFT Modeling and Visualization of the Reaction Mechanisms

Serendipitous Synthesis Found in the Nuances of Homoleptic Zinc Complex Formation

DFT Visualization and Experimental Evidence of BHT-Mg-Catalyzed Copolymerization of Lactides, Lactones and Ethylene Phosphates

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