Syntheses of Dendrimer-type Model Complexes of Non-heme Enzyme Having an Ability on Alkane Oxidation

具有烷烃氧化能力的非血红素酶树枝状模型复合物的合成

基本信息

  • 批准号:
    14540518
  • 负责人:
  • 金额:
    $ 1.73万
  • 依托单位:
  • 依托单位国家:
    日本
  • 项目类别:
    Grant-in-Aid for Scientific Research (C)
  • 财政年份:
    2002
  • 资助国家:
    日本
  • 起止时间:
    2002 至 2003
  • 项目状态:
    已结题

项目摘要

Methanemonooxygenase (MMO), one of the Non-heme metalloenzyme, draws much attention due to its high ability on oxygenation of alkanes giving alcohols under mild conditions. Dendrimers having a structure with regularly branching form are spherical single molecular, which resembles to micells, and show characteristic behavior. Although we have already developed good catalysts for alkane oxygenations, the catalytic system had a defect that the catalysts showed high activity only in chlorinated solvents. Introducing dendrons to our ruthenium complexes having high catalytic ability on alkane oxygenation, the solubility of the catalyst is able to be freely controlled and realizes excellent models of MMO.Dendrimer-type ruthenium complexes have been synthesized. One has tetradentate ligand, tris (pyridylmethyl) amine (TPA), and the other has both terdentate ligand, terpyridine, and, bidentate ligand, bipyridine. Dendrons of benzylether type were introduced to their pyridyl groups. First, second, and third generation of the dendrimers were prepared and it was found that they have catalytic ability on alkane oxygenation.In the present catalysts the key inetermediate is assumed to be a five-coordinated species. In general, ruthenium complexes are known to show photochemical activity such as isomerization and/or ligand substitution under irradiation with dissociative mechanism. Preliminary experiments revealed that the ruthenium complexes prepared above showed an activity on photochemical isomerization and/or ligand substitution with good quantum yield.Further, formation of possible five-coordinated species was observed on irradiation of the complexes in chlorinated solvent. The reaction of the five-coordinated intermediate and pyridine N-oxide gave new spieces showing similar UV spectra to those of oxoruthenium complexes reported in literatures. Further studies are in progress.
甲烷单加氧酶(Methanemonooxygenase,MMO)是一种非血红素类金属酶,因其在温和条件下氧化烷烃生成醇类的能力而备受关注。树枝状大分子是一种球形单分子,具有规则的分支结构,类似于胶束,表现出特有的行为。虽然我们已经开发出了良好的烷烃氧化催化剂,但催化体系存在的缺陷是催化剂仅在氯代溶剂中表现出高活性。将树枝状分子引入到对烷烃氧化具有高催化能力的钌配合物中,可以自由控制催化剂的溶解度,实现了MMO的优良模型。一个具有四齿配体三(吡啶甲基)胺(TPA),另一个具有三齿配体三联吡啶和双齿配体联吡啶。苄基醚型树枝状分子被引入到它们的吡啶基上。制备了第一、二、三代树枝状大分子,发现它们对烷烃氧化反应具有催化活性。一般来说,已知钌络合物在辐射下以解离机制显示光化学活性,例如异构化和/或配体取代。初步实验表明,所合成的钌配合物具有良好的光化学异构化和/或配体取代活性,并在氯化溶剂中有可能形成五配位物种.该五配位中间体与吡啶氮氧化物反应,得到了与文献报道的钌氧配合物相似的紫外光谱。进一步的研究正在进行中。

项目成果

期刊论文数量(7)
专著数量(0)
科研奖励数量(0)
会议论文数量(0)
专利数量(0)
Motowo Yamaguchi(他3名): "Photoassisted Oxygenation of Alkane Catalyzed by Ruthenium Complexes Using 2,6-Dichloropyridine N-Oxide under Visible Light Irradiation"Chemical Communications. 798-799 (2004)
Motowo Yamaguchi(和其他 3 人):“在可见光照射下使用 2,6-二氯吡啶 N-氧化物催化烷烃的光辅助氧化”Chemical Communications 798-799 (2004)。
  • DOI:
  • 发表时间:
  • 期刊:
  • 影响因子:
    0
  • 作者:
  • 通讯作者:
Motowo Yamaguchi (他3名): "Photoassisted Oxygenation of Alkane Catalyzed by Ruthenium Complexes Using 2,6-Dichloropyridine N-Oxide under Visible Light Irradiation"Chemical Communications. (印刷中). (2004)
Motowo Yamaguchi(和其他 3 人):“在可见光照射下使用 2,6-二氯吡啶 N-氧化物催化烷烃的光辅助氧化”(出版中)。
  • DOI:
  • 发表时间:
  • 期刊:
  • 影响因子:
    0
  • 作者:
  • 通讯作者:
Dai Masui(他2名): "trans(Cl, N_<amino>-Chloro(dimethyl sulfoxide-κS)[tris(2-pyridylmethyl)amine-κ^4N]ruthenium(II) trichlorotris(dimethyl sulfoxide-κS)ruthenate(II)"Acta Crystallography Sect E. E59. m308-m309 (2003)
Dai Masui (其他 2 人):“反式(Cl, N_<氨基>-氯(二甲亚砜-κS)[三(2-吡啶甲基)胺-κ^4N]钌(II)三氯三(二甲亚砜-κS)钌酸( II)《晶体学学报E.E59.m308-m309(2003)
  • DOI:
  • 发表时间:
  • 期刊:
  • 影响因子:
    0
  • 作者:
  • 通讯作者:
Motowo Yamaguchi, Takashi Kumano, Dai Masui, Takamichi Yamagishi: "Photoassisted Oxygenation of Alkane Catalyzed by Ruthenium Complexes Using 2,6-Dichloropyridine N-Oxide under Visible Light Irradiation"Chemical Communications. 798-799 (2004)
Motowo Yamaguchi、Takashi Kumano、Dai Masui、Takamichi Yamagishi:“可见光照射下使用 2,6-二氯吡啶 N-氧化物的钌配合物催化烷烃的光辅助氧化”化学通讯。
  • DOI:
  • 发表时间:
  • 期刊:
  • 影响因子:
    0
  • 作者:
  • 通讯作者:
Dai Masui, Motowo Yamaguchi, Takamichi Yamagishi: "trans(CI,Namino)-Chloro(dimethyl sulfoxide-κS) [tris(2-pyridylmethyl) amine-κ^4N]ruthenium(II) trichlorotris(dimethyl sulfoxide-κS) ruthenate(II)"Acta Crystallography Sect E.. E59. m308-m309 (2004)
Dai Masui、Motowo Yamaguchi、Takamichi Yamagishi:“反式(CI,Namino)-氯(二甲亚砜-κS)[三(2-吡啶甲基)胺-κ^4N]三氯三(二甲亚砜-κS)钌酸钌(II)( II)《晶体学学报E..E59.m308-m309(2004)
  • DOI:
  • 发表时间:
  • 期刊:
  • 影响因子:
    0
  • 作者:
  • 通讯作者:
{{ item.title }}
{{ item.translation_title }}
  • DOI:
    {{ item.doi }}
  • 发表时间:
    {{ item.publish_year }}
  • 期刊:
  • 影响因子:
    {{ item.factor }}
  • 作者:
    {{ item.authors }}
  • 通讯作者:
    {{ item.author }}

数据更新时间:{{ journalArticles.updateTime }}

{{ item.title }}
  • 作者:
    {{ item.author }}

数据更新时间:{{ monograph.updateTime }}

{{ item.title }}
  • 作者:
    {{ item.author }}

数据更新时间:{{ sciAawards.updateTime }}

{{ item.title }}
  • 作者:
    {{ item.author }}

数据更新时间:{{ conferencePapers.updateTime }}

{{ item.title }}
  • 作者:
    {{ item.author }}

数据更新时间:{{ patent.updateTime }}

YAMAGUCHI Motoo其他文献

YAMAGUCHI Motoo的其他文献

{{ item.title }}
{{ item.translation_title }}
  • DOI:
    {{ item.doi }}
  • 发表时间:
    {{ item.publish_year }}
  • 期刊:
  • 影响因子:
    {{ item.factor }}
  • 作者:
    {{ item.authors }}
  • 通讯作者:
    {{ item.author }}

{{ truncateString('YAMAGUCHI Motoo', 18)}}的其他基金

Development of on-off controllable photochromic dinuclear ruthenium complexes by redox switch
氧化还原开关开关可控光致变色双核钌配合物的研制
  • 批准号:
    22550062
  • 财政年份:
    2010
  • 资助金额:
    $ 1.73万
  • 项目类别:
    Grant-in-Aid for Scientific Research (C)
ynthesis of Macrocyclic Multinuclear Ruthenium Complexes Having an Ability on Catalytic Oxidation by Self-Assembly
自组装合成具有催化氧化能力的大环多核钌配合物
  • 批准号:
    12640544
  • 财政年份:
    2000
  • 资助金额:
    $ 1.73万
  • 项目类别:
    Grant-in-Aid for Scientific Research (C)
{{ showInfoDetail.title }}

作者:{{ showInfoDetail.author }}

知道了