Understanding the Polymerization of Diphenylacetylenes with Tantalum(V) Chloride and Cocatalysts: Production of Cyclic Poly(diphenylacetylene)s by Low-Valent Tantalum Species Generated in Situ

被引：14

作者：

Sueyoshi, Shingyo ^{[1
]}

Taniguchi, Tsuyoshi ^{[2
]}

Tanaka, Saki ^{[2
]}

Asakawa, Hitoshi ^{[3
,4
]}

Nishimura, Tatsuya ^{[2
]}

Maeda, Katsuhiro ^{[2
,4
]}

机构：

[1] Kanazawa Univ, Grad Sch Frontier Sci Initiat, Kanazawa, Ishikawa 9201192, Japan

[2] Kanazawa Univ, Grad Sch Nat Sci & Technol, Kanazawa, Ishikawa 9201192, Japan

[3] Kanazawa Univ, Grad Sch Nat Sci & Technol, Nanomat Res Inst NanoMaRi, Kanazawa, Ishikawa 9201192, Japan

[4] Kanazawa Univ, Nano Life Sci Inst WPI NanoLSI, Kanazawa, Ishikawa 9201192, Japan

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2021年 / 143卷 / 39期

关键词：

WCL6 BASED INITIATORS; METATHESIS POLYMERIZATION; SUBSTITUTED ACETYLENES; ORGANOMETALLIC COCATALYSTS; DISUBSTITUTED ACETYLENES; ALKYLIDENE COMPLEXES; 4+2 CYCLOADDITION; ALKYNE COMPLEXES; RECENT PROGRESS; POLYMERS;

D O I：

10.1021/jacs.1c06811

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

A systematic investigation of the polymerization of representative diphenylacetylenes with TaCl5 and cocatalysts suggested that low-valent Ta species, which are formed by in situ reduction of TaCl5 by the cocatalysts, are involved in the polymerization and that the polymerization reaction proceeds by an insertion ring expansion mechanism via the formation of tantalacyclopentadiene intermediates, rather than the previously considered metathesis mechanism. This polymerization mechanism indicates the production of unprecedented cis-stereoregular cyclic poly(diphenylacetylene)s. Indeed, the possibilities of a cyclic structure and high cis-stereoregularity of the resulting polymers were reasonably supported by the results of their detailed atomic force microscopy (AFM) and NMR analyses, respectively.

引用

页码：16136 / 16146

页数：11