High Temperature Ring Opening Metathesis Polymerization (ROMP) of Low Strained Cycloheptene and Cis-Cyclooctene by (Arylimido)Niobium(V)–Alkylidene Catalysts

HAMAKAWA Nao, CHATCHAIPAIBOON Kanchana, NOMURA Kotohiro

doi:10.1627/jpi.67.176

Bibliographic Information

Other Title

芳香族イミド配位ニオブ(V)–アルキリデン触媒によるシクロヘプテンやcis-シクロオクテンの高温開環メタセシス重合

Description

Ring opening metathesis polymerization (ROMP) of cycloheptene (CHPE) and cis-cyclooctene (COE) was investigated using (arylimido)niobium(V) catalysts containing the fluorinated alkoxide ligands, Nb(CHSiMe₃)(NAr)[OC(CF₃)₃](PMe₃)₂ (Ar = 2,6-Cl₂C₆H₃, C₆H₅, 2,6-F₂C₆H₃, C₆F₅), and their halogenated phenoxide analogues, Nb(CHSiMe₃)(N-2,6-Cl₂C₆H₃)(OC₆F₅)(PMe₃)₂, Nb(CHSiMe₃)(NAr)(OC₆Cl₅)(PMe₃)₂ [Ar = 2,6-F₂C₆H₃, C₆F₅]. Nb(CHSiMe₃)(NC₆F₅)(OC₆Cl₅)(PMe₃)₂ exhibited superior catalytic activity for ROMP of COE especially at 80 °C and 100 °C [ex. TOF 18,900 h⁻¹ (5.26 s⁻¹) after 2 min at 100 °C], and the polymerizations proceeded in a living manner without catalyst deactivation. Cis-specific ROMPs of CHPE and COE were demonstrated by Nb(CHSiMe₃)(NC₆H₅)[OC(CF₃)₃](PMe₃)₂ and the activities increased at 80 °C, but certain degree of second metathesis (presumably backbiting) also occurred in the ROMP of CHPE even at 80 °C and in the ROMP of COE at 50 °C.

Journal

Journal of the Japan Petroleum Institute

Journal of the Japan Petroleum Institute 67 (5), 176-185, 2024-09-01

The Japan Petroleum Institute

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Details 詳細情報について

CRID: 1390301375025741952

DOI: 10.1627/jpi.67.176

ISSN: 1349273X; 13468804

Web Site: https://www.jstage.jst.go.jp/article/jpi/67/5/67_176/_pdf

Text Lang: ja

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High Temperature Ring Opening Metathesis Polymerization (ROMP) of Low Strained Cycloheptene and <i>Cis</i>-Cyclooctene by (Arylimido)Niobium(V)–Alkylidene Catalysts