A STUDY ON CATALYTIC ACTIVITIES OF ORGANOMETALLIC COMPLEXES BEARING TRIS (PYRAZOLYL) BORATE LIGANDS

含三(吡唑基)硼酸酯配体的有机金属配合物催化活性的研究

• 批准号: 08455432
• 负责人: OZAWA Fumiyuki
• 金额: $ 1.54万
• 依托单位: OSAKA CITY UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 1996
• 资助国家: 日本
• 起止时间: 1996 至 1997
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-08455432/
• 关键词: Tris (pyrazolyl) borate; Alkylruthenium complexes; (pi-allyl) rhodium complexes; Catalysts for acetylene polymerization; Catalysts for metathesis polymerization

1.Stereoregular Polymerization of Phenylacetylenes Catalyzed by [Hydrotris (pyrazolyl) borato] rhodium ComplexesRhodium (I) tris (pyrazolyl) borate complexes Tp^<R2>Rh (cod) (R=Me, Ph, i-Pr) were found to serve as efficient catalysts for highly stereoregular polymerization of phenylacetylene derivatives (p-YC_6H_4C=CH : Y=H,Me, Cl, CN,CO_2Me, COMe, NO_2) to give poly (phenylacetylene) s having a head-to-tail, cis-transoidal structure.2.Ring-opening Metathesis Polymerization of Norbornene Derivatives Catalyzed by Vinylideneruthenium ComplexesA vinylideneruthenium complex bearing a hydrotris (pyrazolyl) borate ligand serves as a good catalyst precursor for the ring-opening metathesis polymerization of norbornene derivatives. The catalytic activity is efficiently enhanced by adding Lewis acid such as BF_3・Et_2O to the system. The catalytic activities of related vinylidene complexes having tertiary phosphine ligands are also examined.3.Synthesis and Reactions of (pi-Allyl) bromo [hydrotris (3,5-dimethylpyrazolyl) borato] rthodiumThe complex Tp^<Me2>Rh (coe) (MeCN) has been found to undergo the oxidative addition of allyl bromide to give a pi-allyl complex Tp^<Me2>Rh (pi-allyl) Br, which exhibits high reactivity toward MeMgBr and Li [BHE_<t3>] to give Tp^<Me2>Rh (pi-allyl) Me and Tp^<Me2>Rh (pi-allyl) H,respectively. The latter is formed mainly by nucleophilic addition of H-to the central carbon of the pi-allyl ligand followed by beta-hydrogen elimination of the resultant rhodacyclobutane intermediate.4.Synthesis of Alkyl [hydrotris (pyrazolyl) borato] ruthenium (II) Complexes by TransmetallationAlkylation of [Ru (tp) Cl (cod)] (Tp=hydrotris (pyrazolyl) borate) with AlR_3 (R=Et, Me) successfully proceeded in a benzene or toluene solution at room temperature to give the corresponding [Ru (tp) R (cod)] complexes (R=Et, Me) in high yields.

1.[Hydrotris(pyrazolyl)borato]铑配合物催化苯乙炔的立构聚合反应铑(I)三(吡唑基)硼酸配合物Tp^<R2>Rh(cod)(R=Me,Ph,i-Pr)被发现可作为苯乙炔衍生物高度立构规整聚合的有效催化剂 (p-YC_6H_4C=CH : Y=H,Me, Cl, CN,CO_2Me, COMe, NO_2) 得到具有头尾顺式反式结构的聚苯乙炔。 2. 亚乙烯基钌配合物催化降冰片烯衍生物的开环复分解聚合带有水三的亚乙烯基钌配合物 (吡唑基)硼酸酯配体是降冰片烯衍生物开环易位聚合的良好催化剂前体。通过在体系中添加BF_3·Et_2O等路易斯酸，可以有效提高催化活性。还考察了具有叔膦配体的相关亚乙烯基配合物的催化活性。 3.(pi-烯丙基)溴[氢化三(3,5-二甲基吡唑基)硼]铑的合成与反应配合物Tp^<Me2>Rh(coe)(MeCN)经烯丙基溴氧化加成得到 pi-烯丙基配合物Tp^<Me2>Rh (pi-烯丙基) Br，对MeMgBr和Li [BHE_<t3>]表现出高反应性，分别生成Tp^<Me2>Rh (pi-烯丙基) Me和Tp^<Me2>Rh (pi-烯丙基) H。后者主要是通过将 H- 亲核加成到 pi-烯丙基配体的中心碳上，然后将所得的铑环丁烷中间体进行 β-氢消除而形成。 4. 通过 [Ru (tp) Cl (cod)] 的金属转移烷基化合成烷基 [Hydrotris (pyrazolyl) borato] 钌 (II) 配合物 (Tp=Hydrotris) (吡唑基)硼酸酯)与AlR_3 (R=Et, Me)在苯或甲苯溶液中在室温下成功反应，以高产率得到相应的[Ru (tp) R (cod)]络合物(R=Et, Me)。

项目成果

丸山 洋一郎: "Synthesis of Alkyl[hydrotris(pyrazolyl)borato]ruthenium(II)Complexes by Transmetallation" Bull.Chem.Soc.Jpn.70・3. 689-693 (1997)

Yoichiro Maruyama：“通过金属转移合成烷基[氢三(吡唑基)硼酸]钌(II)络合物”Bull.Chem.Soc.Jpn.70・3 (1997)。

片山 博之: "Stereoregular Polymerization of Phenylacetylenes Catalyzed by [Hydrotris-(pyrazolyl)borato]rhodium(I)Complexes" Organometallics. 16・20. 4497-4500 (1997)

Hiroyuki Katayama：“[Hydrotris-(吡唑基)硼酸]铑(I)配合物催化的苯乙炔的立构聚合”有机金属学16・20 (1997)。

片山 博之: "Ring-opening metathesis polymerization of norbornene catalyzed by[Hydridotris(pyrazolyl)borato]vinylideneruthenium(II)complex" J.Organomet.Chem.(印刷中). (1998)

Hiroyuki Katayama：“[氢化三(吡唑基)硼酸]亚乙烯基钌(II)复合物催化的降冰片烯开环复分解聚合”J.Organomet.Chem.（出版中）。

H Katayama: ""The New Possibility of Vinylideneruthenium (II) Complexes Derived from Terminal Alkynes : Ring-Opening Metathesis Polymerization of Norbornene Derivatives"" Chem.Lett.(1). 67-68 (1998)

H Katayama：“由末端炔烃衍生的亚乙烯基钌 (II) 配合物的新可能性：降冰片烯衍生物的开环复分解聚合”，Chem.Lett.(1)。

片山 博之: "The New Possibility of Vinylideneruthenium(II)Complexes Derived from Terminal Alkynes:Ring-Opening Metathesis Polymerization of Norbornene Derivatives" Chem.Lett.1. 67-68 (1998)

Hiroyuki Katayama：“由末端炔烃衍生的乙烯基钌(II)络合物的新可能性：降冰片烯衍生物的开环复分解聚合”Chem.Lett.1 (1998)。