Living Metathesis and Metallotropy Polymerization Gives Conjugated Polyenynes from Multialkynes: How to Design Sequence-Specific Cascades for Polymers

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Title
Living Metathesis and Metallotropy Polymerization Gives Conjugated Polyenynes from Multialkynes: How to Design Sequence-Specific Cascades for Polymers
Author(s)
Cheol Kang; Seongyeon Kwon; Jong-Chan Sung; Jinwoo Kim; Mu-Hyun Baik; Tae-Lim Choi
Publication Date
2018-11
Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, v.140, no.47, pp.16320 - 16329
Publisher
AMER CHEMICAL SOC
Abstract
On the basis of a combined experimental and computational study, a novel method for preparing fully conjugated polyenynes via cascade metathesis and metallotropy (M&M) polymerization of various multialkynes is developed. DFT calculations elucidate the detailed mechanism of the metallotropic 1,3-shift, which is a key process of M&M polymerization. An ��,��-(C,C,C)-agostic interaction stabilizing the metallacyclobutadiene transition state is found to be critically important for the successful polymerization with excellent specificity. The polymerization efficiency displayed by the tetrayne monomer is controlled by the steric demands of its substituents, and more complex hexayne monomers can be successfully polymerized to give access to highly conjugated polyenynes via a series of intramolecular metathesis and metallotropic shift cascade reactions. Furthermore, living polymerization led to the synthesis of block copolymers consisting of fully conjugated polyenyne backbones. The implementation of pentayne monomers provides polyenynes with successive C-C triple bonds via consecutive metallotropic 1,3-shift. In short, the design of multialkynes enables the preparation of diverse conjugated polyenyne motifs via selective M&M cascade reactions. Copyright © 2018 American Chemical Society
URI
https://pr.ibs.re.kr/handle/8788114/5393
ISSN
0002-7863
Appears in Collections:
Center for Catalytic Hydrocarbon Functionalizations(분자활성 촉매반응 연구단) > Journal Papers (저널논문)
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