Proposed Mechanism for the High-Yield Polymerization of Oxyethyl Propiolates with Rh Complex Catalyst Using the Density Functional Theory Method

In this study, poly(oxyethyl propiolate)s (POP)s featuring various oxyethylene derivatives are synthesized using a [Rh(norbornadiene)Cl](2) catalyst. In particular, POPs featuring the normal oxyethylene chain in the side-chain exhibit excellent yields and high molecular weights in methanol and N,N-d...

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Autores principales: Yoshida, Yoshiaki, Mawatari, Yasuteru, Tabata, Masayoshi
Formato: Online Artículo Texto
Lenguaje:English
Publicado: MDPI 2019
Materias:
Article
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6402018/
https://www.ncbi.nlm.nih.gov/pubmed/30960077
http://dx.doi.org/10.3390/polym11010093
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author Yoshida, Yoshiaki
Mawatari, Yasuteru
Tabata, Masayoshi
author_facet Yoshida, Yoshiaki
Mawatari, Yasuteru
Tabata, Masayoshi
author_sort Yoshida, Yoshiaki
collection PubMed
description In this study, poly(oxyethyl propiolate)s (POP)s featuring various oxyethylene derivatives are synthesized using a [Rh(norbornadiene)Cl](2) catalyst. In particular, POPs featuring the normal oxyethylene chain in the side-chain exhibit excellent yields and high molecular weights in methanol and N,N-dimethylformamide at 40 °C, compared with poly(n-alkyl propiolate)s (PnAP)s. The high reactivity of the oxyethyl propiolate (OP) monomers is clarified by considering the time dependences of the polymerization yields of OPs and alkyl propiolates (Aps). Furthermore, the monomer structure and intermediate conformation of the Rh complex are optimized using Density Function theory (DFT) methods (B3LYP/6-31G** and B3LYP/LANL2DZ) and a polymerization mechanism is proposed.
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spelling pubmed-64020182019-04-02 Proposed Mechanism for the High-Yield Polymerization of Oxyethyl Propiolates with Rh Complex Catalyst Using the Density Functional Theory Method Yoshida, Yoshiaki Mawatari, Yasuteru Tabata, Masayoshi Polymers (Basel) Article In this study, poly(oxyethyl propiolate)s (POP)s featuring various oxyethylene derivatives are synthesized using a [Rh(norbornadiene)Cl](2) catalyst. In particular, POPs featuring the normal oxyethylene chain in the side-chain exhibit excellent yields and high molecular weights in methanol and N,N-dimethylformamide at 40 °C, compared with poly(n-alkyl propiolate)s (PnAP)s. The high reactivity of the oxyethyl propiolate (OP) monomers is clarified by considering the time dependences of the polymerization yields of OPs and alkyl propiolates (Aps). Furthermore, the monomer structure and intermediate conformation of the Rh complex are optimized using Density Function theory (DFT) methods (B3LYP/6-31G** and B3LYP/LANL2DZ) and a polymerization mechanism is proposed. MDPI 2019-01-08 /pmc/articles/PMC6402018/ /pubmed/30960077 http://dx.doi.org/10.3390/polym11010093 Text en © 2019 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (http://creativecommons.org/licenses/by/4.0/).
spellingShingle Article
Yoshida, Yoshiaki
Mawatari, Yasuteru
Tabata, Masayoshi
Proposed Mechanism for the High-Yield Polymerization of Oxyethyl Propiolates with Rh Complex Catalyst Using the Density Functional Theory Method
title Proposed Mechanism for the High-Yield Polymerization of Oxyethyl Propiolates with Rh Complex Catalyst Using the Density Functional Theory Method
title_full Proposed Mechanism for the High-Yield Polymerization of Oxyethyl Propiolates with Rh Complex Catalyst Using the Density Functional Theory Method
title_fullStr Proposed Mechanism for the High-Yield Polymerization of Oxyethyl Propiolates with Rh Complex Catalyst Using the Density Functional Theory Method
title_full_unstemmed Proposed Mechanism for the High-Yield Polymerization of Oxyethyl Propiolates with Rh Complex Catalyst Using the Density Functional Theory Method
title_short Proposed Mechanism for the High-Yield Polymerization of Oxyethyl Propiolates with Rh Complex Catalyst Using the Density Functional Theory Method
title_sort proposed mechanism for the high-yield polymerization of oxyethyl propiolates with rh complex catalyst using the density functional theory method
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6402018/
https://www.ncbi.nlm.nih.gov/pubmed/30960077
http://dx.doi.org/10.3390/polym11010093
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AT tabatamasayoshi proposedmechanismforthehighyieldpolymerizationofoxyethylpropiolateswithrhcomplexcatalystusingthedensityfunctionaltheorymethod

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