CREATION AND CATALYTIC PROPERTIES OF ORGANOTRANSITION METAL COMPLEXES BEARING PHOSPHAALKENE LIGANDS

含磷烯配体有机过渡金属配合物的制备及其催化性能

基本信息

  • 批准号:
    15350060
  • 负责人:
  • 金额:
    $ 9.15万
  • 依托单位:
  • 依托单位国家:
    日本
  • 项目类别:
    Grant-in-Aid for Scientific Research (B)
  • 财政年份:
    2003
  • 资助国家:
    日本
  • 起止时间:
    2003 至 2005
  • 项目状态:
    已结题

项目摘要

(1)Electronic and steric properties of 1,2-diaryl-3,4-bis(2,4,6-tri-t-butylphenylphosphinidene)cyclobutene ligands [aryl=4-methoxyphenyl (DPCB-OMe) ; phenyl (DPCB) ; 4-trifluoromethylphenyl (DPCB-CF_3)] have been investigated using their methylplatinum(II) and palladium(II) complexes. It has been found that DPCB-Y ligands possess intermediate magnitude of σ-donating ability between common diimine and diphosphine ligands, but be much stronger π-acceptors than the other supporting ligands.(2)The mechanism of dehydrative condensation of allylic alcohols and aniline (i.e. N-allylation of aniline) catalyzed by palladium DPCB-OMe complex has been examined by model studies of possible intermediates as well as kinetic investigations. A novel process involving a hydridopalladium intermediate has been proposed for C-O bond cleavage of allylic alcohol to give (π-allyl)palladium complexes.(3)(π-Allyl)palladium triflate bearing DPCB-OMe ligand efficiently catalyzes deallylation of a variety of ally … More l ethers in aniline to give corresponding alcohols in high yields under mild conditions. The same complex serves as a highly active catalyst for cyclodehydration of cis-2-butene-1,4-diol with active methylene compounds to give 2-vinyl-2,3-dihydrofurans.(4)Cationic complexes of the formula [Pd(MeCN)_2(DPCB-Y)](OTf)_2 and [Rh(MeCN)_2(DPCB-Y)](OTf) have been prepared. The former shows high catalytic activity towards conjugate addition of benzyl carbamate to α,β-unsaturated ketones.(5)Palladium or copper complexes bearing DPCB catalyze cross-coupling of aryl halides with anilines, organotin reagents, or zinc cyanide.(6)Dichlororuthenium complex bearing DPCB-OMe ligand catalyzes highly stereoselective hydrosilylation of diethynylarenes with HSiMe_2Ph to give (Z,Z)-bis(2-silylethenyl)arenes. Treatment of the hydrosilylation products with NBS causes bromodesilylation in a stereospecific manner, giving (Z,Z)-bis(2-bromoethenyl)arenes with high geometrical purities (>98%). (Z,Z)-Bis(2-bromoethenyl)benzenes thus obtained have been applied to the synthesis of geometrically pure all-cis poly(phenylene vinylene)s (PPVs), which are synthesized by Suzuki-Miyaura-type polycondensation with 2,5-dioctyloxy-1,4-benzenediboronic acid. The all-cis PPVs undergo one-way photoisomerization to the corresponding trans-PPVs both in solution and in the solid. This phenomenon is applied to direct microscale patterning of PPVs onto a quartz substrate. Less
(1)用1,2-二芳基-3,4-双(2,4,6-三叔丁基苯基膦)环丁烯配体[芳基=4-甲氧基苯基(DPCB-OMe);苯基(DCB); 4-三氟甲基苯基(DPCB-CF_3)]的甲基铂(II)和钯(II)配合物研究了它们的电子和空间性质。结果表明,DPCB-Y配体的σ-供电子能力介于一般的双亚胺和双膦配体之间,但其π-受体能力远强于其它的配体。(2)通过对可能的中间体的模型研究和动力学研究,探讨了钯-DPCB-OMe配合物催化烯丙醇与苯胺脱水缩合反应(即苯胺的N-烯丙基化反应)的机理。本文提出了一种以烯丙醇为原料,以钯为中间体,通过C-O键裂解制备(π-烯丙基)钯配合物的新方法。(3)(含DPCB-OMe配体的三氟甲磺酸(π-烯丙基)钯催化剂能有效地催化多种烯丙基的脱烯丙基化反应 ...更多信息 在温和的条件下,以较高的产率得到相应的醇。该配合物可作为顺式-2-丁烯-1,4-二醇与活性亚甲基化合物环化脱水生成2-乙烯基-2,3-二氢呋喃的高活性催化剂。(4)合成了配合物[Pd(MeCN)_2(DPCB-Y)](OTf)_2和[Rh(MeCN)_2(DPCB-Y)](OTf)。前者对氨基甲酸苄酯与α,β-不饱和酮的共轭加成反应表现出较高的催化活性。(5)带有DPCB的钯或铜络合物催化芳基卤化物与苯胺、有机锡试剂或氰化锌的交叉偶联。(6)含DPCB-OMe配体的二氯钌配合物催化二乙炔基芳烃与HSiMe_2Ph的高立体选择性硅氢加成反应,合成了(Z,Z)-双(2-硅基乙烯基)芳烃。用NBS处理氢化硅烷化产物以立体定向方式引起溴脱甲硅烷基化,得到具有高几何纯度(>98%)的(Z,Z)-双(2-溴乙烯基)芳烃。将所得到的(Z,Z)-双(2-溴乙烯基)苯用于合成几何纯的全顺式聚对苯乙炔(PPV),并与2,5-二辛氧基-1,4-苯二硼酸通过Suzuki-Miyaura型缩聚反应合成了PPV。全顺式PPV在溶液和固体中均发生单向光异构化,生成相应的反式PPV。这种现象被应用到直接的PPV到石英衬底上的微尺度图案化。少

项目成果

期刊论文数量(43)
专著数量(0)
科研奖励数量(0)
会议论文数量(0)
专利数量(0)
Catalytic C-O Bond Cleavage of Allylic Alcohols using Diphosphinidenecyclobutene-coordinated Palladium Complexes. Mechanistic Study
使用二膦亚基环丁烯配位钯配合物催化烯丙醇的 C-O 键断裂。
  • DOI:
  • 发表时间:
    2004
  • 期刊:
  • 影响因子:
    0
  • 作者:
    F;Ozawa;H;Katayama;K.Toyota;M.Yoshifuji;R.S.Jensen;長尾将人;A.S.Gajare;片山博之;小澤文幸;小澤文幸
  • 通讯作者:
    小澤文幸
Application of a diphosphinidenecyclobutene ligand in the solvent-free copper-catalysed amination reactions of aryl halides
  • DOI:
    10.1039/b408232j
  • 发表时间:
    2004-01-01
  • 期刊:
  • 影响因子:
    4.9
  • 作者:
    Gajare, AS;Toyota, K;Ozawa, F
  • 通讯作者:
    Ozawa, F
Facile and Selective Deallylation of Allylic Compounds using Diphosphinidenecyclobutene-coordinated Palladium Catalysts
使用二膦亚基环丁烯配位钯催化剂轻松选择性地对烯丙基化合物进行脱烯丙基化
  • DOI:
  • 发表时间:
    2004
  • 期刊:
  • 影响因子:
    0
  • 作者:
    H.Murakami;T.Minami;F Ozawa
  • 通讯作者:
    F Ozawa
Stereoselective Synthesis of cis- and trans-Oligo(phenylenevinylene)s via Palladium-Catalyzed Cross-Coupling Reactions
通过钯催化交叉偶联反应立体选择性合成顺式和反式寡聚(亚苯基亚乙烯基)
sp^2混成リン配位子をもつ特異な遷移金属錯体触媒
独特的具有sp^2杂化磷配体的过渡金属配合物催化剂
  • DOI:
  • 发表时间:
    2005
  • 期刊:
  • 影响因子:
    0
  • 作者:
    H.Tsukamoto;M.Sato;Y.Kondo;Akitake Nakamura;Anil S.Gajare;Subaru Kawasaki;Subaru Kawasaki;Akitake Nakamura;Subaru Kawasaki;Rader S.Jensen;小澤文幸
  • 通讯作者:
    小澤文幸
{{ 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 }}

OZAWA Fumiyuki其他文献

OZAWA Fumiyuki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('OZAWA Fumiyuki', 18)}}的其他基金

Study of Cross-Coupling Reactions for Precisely Controlled Synthesis of π-Conjugated Polymers
π-共轭聚合物精确控制合成的交叉偶联反应研究
  • 批准号:
    20350049
  • 财政年份:
    2008
  • 资助金额:
    $ 9.15万
  • 项目类别:
    Grant-in-Aid for Scientific Research (B)
Functional Transition Metal Complexes with Heavier Element Ligands
具有重元素配体的功能性过渡金属配合物
  • 批准号:
    18064010
  • 财政年份:
    2006
  • 资助金额:
    $ 9.15万
  • 项目类别:
    Grant-in-Aid for Scientific Research on Priority Areas
Reaction Control of Dynamic Complexes Relevant to Catalysis
与催化相关的动态配合物的反应控制
  • 批准号:
    14078222
  • 财政年份:
    2002
  • 资助金额:
    $ 9.15万
  • 项目类别:
    Grant-in-Aid for Scientific Research on Priority Areas
REACTION CONTROL OF ORGANOMETALLIC COMPLEXES RELEVANT TO CATALYTIC HYDROSILYLATION
催化氢化硅烷化相关有机金属配合物的反应控制
  • 批准号:
    12450367
  • 财政年份:
    2000
  • 资助金额:
    $ 9.15万
  • 项目类别:
    Grant-in-Aid for Scientific Research (B)
The Chemistry of Linkages between Main Group Elements and Transition Metals
主族元素与过渡金属键合的化学
  • 批准号:
    09239105
  • 财政年份:
    1997
  • 资助金额:
    $ 9.15万
  • 项目类别:
    Grant-in-Aid for Scientific Research on Priority Areas
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
  • 财政年份:
    1996
  • 资助金额:
    $ 9.15万
  • 项目类别:
    Grant-in-Aid for Scientific Research (B)

相似海外基金

Spectroscopic and Mechanistic Studies of Odd-Electron Palladium Complexes
奇电子钯配合物的光谱和机理研究
  • 批准号:
    2102544
  • 财政年份:
    2021
  • 资助金额:
    $ 9.15万
  • 项目类别:
    Continuing Grant
Synthesis and design of palladium complexes to access new substrate classes in coupling reactions
钯配合物的合成和设计,以在偶联反应中获得新的底物类别
  • 批准号:
    540824-2019
  • 财政年份:
    2019
  • 资助金额:
    $ 9.15万
  • 项目类别:
    University Undergraduate Student Research Awards
photopolymerization switching by light-sensitive palladium complexes
光敏钯配合物的光聚合开关
  • 批准号:
    16H04121
  • 财政年份:
    2016
  • 资助金额:
    $ 9.15万
  • 项目类别:
    Grant-in-Aid for Scientific Research (B)
Regioselective functionalization of C-H bonds by dinuclear carboxy palladium complexes
双核羧基钯配合物对 C-H 键的区域选择性功能化
  • 批准号:
    16K05770
  • 财政年份:
    2016
  • 资助金额:
    $ 9.15万
  • 项目类别:
    Grant-in-Aid for Scientific Research (C)
Synthesis of Glucosamine Introduced Platinum and Palladium Complexes and Their Anti-Cancer Activities Based on Heteroatom Chemistry
基于杂原子化学的氨基葡萄糖引入铂钯配合物的合成及其抗癌活性
  • 批准号:
    26410056
  • 财政年份:
    2014
  • 资助金额:
    $ 9.15万
  • 项目类别:
    Grant-in-Aid for Scientific Research (C)
Square planar platinum and palladium complexes of tridentate carbazole-based ligands as SPECT agents
作为 SPECT 试剂的三齿咔唑基配体的方形平面铂和钯配合物
  • 批准号:
    436734-2012
  • 财政年份:
    2012
  • 资助金额:
    $ 9.15万
  • 项目类别:
    Engage Grants Program
New Palladium Complexes with a Series of 2-(1H-imidazol-2-yl)phenol ligands: Syntheses, Structures and Suzuki-Miyaura Catalysis Studies
具有一系列 2-(1H-咪唑-2-基)苯酚配体的新型钯配合物:合成、结构和 Suzuki-Miyaura 催化研究
  • 批准号:
    216373444
  • 财政年份:
    2011
  • 资助金额:
    $ 9.15万
  • 项目类别:
    Research Grants
Strategies for Tailoring the Redox Properties of d6/d8-Electron Platinum and Palladium Complexes
定制 d6/d8-电子铂和钯配合物的氧化还原性能的策略
  • 批准号:
    0749790
  • 财政年份:
    2008
  • 资助金额:
    $ 9.15万
  • 项目类别:
    Continuing Grant
Synthesis, Reaction and Catalysis of Heterodinuclear Alkyl-and Hydridoplatinum(or palladium) Complexes
异双核烷基和氢化铂(或钯)配合物的合成、反应和催化
  • 批准号:
    14078208
  • 财政年份:
    2002
  • 资助金额:
    $ 9.15万
  • 项目类别:
    Grant-in-Aid for Scientific Research on Priority Areas
POWRE: Synthesis of Taxane Diterpenes via Pi-Allyl Palladium Complexes
POWRE:通过 Pi-烯丙基钯配合物合成紫杉烷二萜
  • 批准号:
    0233826
  • 财政年份:
    2002
  • 资助金额:
    $ 9.15万
  • 项目类别:
    Standard Grant
{{ showInfoDetail.title }}

作者:{{ showInfoDetail.author }}

知道了