Rhodium(I) Complexes Bearing an Aryl-Substituted 1,3,5-Hexatriene Chain: Catalysts for Living Polymerization of Phenylacetylene and Potential Helical Chirality of 1,3,5-Hexatrienes

被引：13

作者：

Sakamoto, Shiori ^{[1
]}

Taniguchi, Tsuyoshi ^{[1
]}

Sakata, Yoko ^{[1
]}

Akine, Shigehisa ^{[1
,2
]}

Nishimura, Tatsuya ^{[1
]}

Maeda, Katsuhiro ^{[1
,2
]}

机构：

[1] Kanazawa Univ, Grad Sch Nat Sci & Technol, Kakuma Machi, Kanazawa, Ishikawa 9201192, Japan

[2] Kanazawa Univ, Nano Life Sci Inst WPI NanoLSI, Kakuma Machi, Kanazawa, Ishikawa 9201192, Japan

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2021年 / 60卷 / 41期

关键词：

arene ligands; chirality; helical structures; polymerization; rhodium; ORGANORHODIUM(I) COMPLEXES; ACETYLENIC DERIVATIVES; BOND; INITIATORS; MOCL5; RH;

D O I：

10.1002/anie.202108032

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Unique bench-stable rhodium(I) complexes bearing an aryl-substituted 1,3,5-hexatriene chain have been synthesized by reactions of (bicyclo[2.2.1]hepta-2,5-diene)rhodium(I) chloride dimer ([Rh(nbd)Cl](2)) with aryl boronic acids and diphenylacetylenes in the presence of a 50 % aqueous solution of KOH. X-ray crystallographic analysis of the isolated complexes indicated a square-planar structure stabilized by a strong interaction with one of the aryl groups on the 1,3,5-hexatriene chain, which has a helical structure. The helical chirality of the isolated rhodium complexes was confirmed to be sufficiently stable to be resolved into enantiomers by HPLC on a chiral stationary phase at room temperature. It was confirmed that the isolated rhodium complexes functioned as initiators for living polymerization of phenylacetylene to give cis-stereoregular poly(phenylacetylene) with a well-controlled molecular weight.

引用

页码：22201 / 22206

页数：6

共 4 条

[1] SYNTHESIS AND STRUCTURES OF 1-OXA-3,5-DIAZA-1,3,5-HEXATRIENES - THE 1-OXA-3,5-DIAZA-1,3,5-HEXATRIENE/2H-1,3,5-OXADIAZINE TAUTOMERISM
BUHMANN, M
MOLLER, MH
WURTHWEIN, EU
CHEMISCHE BERICHTE-RECUEIL, 1993, 126 (04): : 957 - 967
[2] 6πe- versus 8πe- Electrocyclization of 1-Aryl- and Heteroaryl-Substituted (1Z,3Z)-1,3,5-Hexatrienes: A Matter of Aromaticity
Garcia-Rubin, Silvia
Varela, Jesus A.
Castedo, Luis
Saa, Carlos
ORGANIC LETTERS, 2009, 11 (04) : 983 - 986
[3] PHOTOCHEMISTRY OF POLYENES .17. - PHOTOCHEMICAL CIS, TRANS ISOMERIZATION OF 3 CYANO-SUBSTITUTED DIPHENYL-1,3-BUTADIENES AND A DIPHENYL-1,3,5-HEXATRIENE - THE DIPOLAR CHARACTER AND THE TORSIONAL POTENTIAL SURFACES OF THE S1 STATE
BARETZ, BH
SINGH, AK
LIU, RSH
NOUVEAU JOURNAL DE CHIMIE-NEW JOURNAL OF CHEMISTRY, 1981, 5 (5-6): : 297 - 303
[4] Synthesis of a Novel Series of Cu(I) Complexes Bearing Alkylated 1,3,5-Triaza-7-phosphaadamantane as Homogeneous and Carbon-Supported Catalysts for the Synthesis of 1-and 2-Substituted-1,2,3-triazoles
Librando, Ivy L.
Mahmoud, Abdallah G.
Carabineiro, Sonia A. C.
Guedes da Silva, M. Fatima C.
Geraldes, Carlos F. G. C.
Pombeiro, Armando J. L.
NANOMATERIALS, 2021, 11 (10)

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