Guidelines To Select the N-Heterocyclic Carbene for the Organopolymerization of Monomers with a Polar Group

Laura Falivene; Luigi Cavallo

doi:10.1021/acs.macromol.6b02646

Guidelines To Select the N-Heterocyclic Carbene for the Organopolymerization of Monomers with a Polar Group

Laura Falivene, Luigi Cavallo

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18 Scopus citations

Abstract

We report on the DFT stability of zwitterion and spirocycle adducts of five polar monomers with nine N-heterocyclic carbenes (NHC), covering the most typical classes of monomers and NHCs used in organopolymerization. Results indicate that the relative stability of the two adducts is dominated by the singlet-triplet energy gap of the free NHC, with low energy gaps favoring the spirocycle adduct, while high energy gaps favor the zwitterionic adduct. This basic structure/property relationship can be tuned by the hindrance of the NHC and the nature of the monomer. In addition to rationalize existing systems, the 45 NHC/monomer combinations we examined can be used as a guideline to predict the behavior of a new NHC/monomer combination.

Original language	English (US)
Pages (from-to)	1394-1401
Number of pages	8
Journal	Macromolecules
Volume	50
Issue number	4
DOIs	https://doi.org/10.1021/acs.macromol.6b02646
State	Published - Feb 13 2017

Bibliographical note

KAUST Repository Item: Exported on 2020-10-01
Acknowledgements: This work was supported by funding from King Abdullah University of Science and Technology (KAUST)

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10.1021/acs.macromol.6b02646

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title = "Guidelines To Select the N-Heterocyclic Carbene for the Organopolymerization of Monomers with a Polar Group",

abstract = "We report on the DFT stability of zwitterion and spirocycle adducts of five polar monomers with nine N-heterocyclic carbenes (NHC), covering the most typical classes of monomers and NHCs used in organopolymerization. Results indicate that the relative stability of the two adducts is dominated by the singlet-triplet energy gap of the free NHC, with low energy gaps favoring the spirocycle adduct, while high energy gaps favor the zwitterionic adduct. This basic structure/property relationship can be tuned by the hindrance of the NHC and the nature of the monomer. In addition to rationalize existing systems, the 45 NHC/monomer combinations we examined can be used as a guideline to predict the behavior of a new NHC/monomer combination.",

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T1 - Guidelines To Select the N-Heterocyclic Carbene for the Organopolymerization of Monomers with a Polar Group

AU - Falivene, Laura

AU - Cavallo, Luigi

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N2 - We report on the DFT stability of zwitterion and spirocycle adducts of five polar monomers with nine N-heterocyclic carbenes (NHC), covering the most typical classes of monomers and NHCs used in organopolymerization. Results indicate that the relative stability of the two adducts is dominated by the singlet-triplet energy gap of the free NHC, with low energy gaps favoring the spirocycle adduct, while high energy gaps favor the zwitterionic adduct. This basic structure/property relationship can be tuned by the hindrance of the NHC and the nature of the monomer. In addition to rationalize existing systems, the 45 NHC/monomer combinations we examined can be used as a guideline to predict the behavior of a new NHC/monomer combination.

AB - We report on the DFT stability of zwitterion and spirocycle adducts of five polar monomers with nine N-heterocyclic carbenes (NHC), covering the most typical classes of monomers and NHCs used in organopolymerization. Results indicate that the relative stability of the two adducts is dominated by the singlet-triplet energy gap of the free NHC, with low energy gaps favoring the spirocycle adduct, while high energy gaps favor the zwitterionic adduct. This basic structure/property relationship can be tuned by the hindrance of the NHC and the nature of the monomer. In addition to rationalize existing systems, the 45 NHC/monomer combinations we examined can be used as a guideline to predict the behavior of a new NHC/monomer combination.

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JO - Macromolecules

JF - Macromolecules

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Guidelines To Select the N-Heterocyclic Carbene for the Organopolymerization of Monomers with a Polar Group

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