Synthesis of Tetranuclear Complexes of Pd and Pt with Planar Structures and Development of Their Functionalities

平面结构Pd和Pt四核配合物的合成及其功能开发

基本信息

  • 批准号:
    16350028
  • 负责人:
  • 金额:
    $ 9.92万
  • 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:
    2004
  • 资助国家:
    日本
  • 起止时间:
    2004 至 2005
  • 项目状态:
    已结题

项目摘要

This research project aims to synthesize novel tetranuclear platinum and palladium complexes having bridging diarylsilylene ligands and to determine the unique planar structures. Dinuclear Pd and Pt complexes with bridging silylene ligands are obtained with the procedure Which were reported by our group as well as the research group in the States. For example, Pt(PCy_3)_2 functions as a convenient precursor of the dinuclear Pt(I) complexes with two bridging silyl ligands. Heterodinuclear Pd-Pt complex with bridging diphenylsilyl ligand is also obtained from a mixture of Pd(O) and Pt(O) complexes. Reaction of a chelating diphosphine ligand with the dinuclear complexes afforded the Pt_4 complexes and Pt_3Pd complexes. The molecular structures of these complexes have been revealed by X-ray crystallography and by detailed NMR measurement of the solutions. The obtained complexes have four Pt(O) or Pd(O) centers bonded with bridging silylene ligands and metal-metal bonding. Bond lengths and angles show high symmetrical planar structures of the complexes. The DFT calculation for the complexes revealed that the tetranuclear core consists of the zero valent metal centers and neutral silylene ligands. Analogous Pd complexes with bridging diarylgermylene ligands have also been prepared and characterized.The above reaction, forming the tetranuclear complexes, has been followed by the NMR spectroscopy. The reaction is induced by exchange of the monodentate phosphine ligand with the chelating diphosphine ligand. The subsequent condensation of the dinuclear complexes accompanies conversion of the silyl ligand to silylene ligand or germyl ligand to digermene ligand, which leads to formation of the tetranuclear complexes.
本课题旨在合成具有桥接二芳基硅烯配体的新型四核铂钯配合物,并确定其独特的平面结构。用本课题组和美国课题组报道的方法制备了带有桥接硅烯配体的双核Pd和Pt配合物。例如,Pt(PCy_3)_2作为具有两个桥接硅基配体的双核Pt(I)配合物的方便前体。Pd(O)和Pt(O)配合物的混合物也可得到带桥接二苯基硅基配体的杂二核Pd-Pt配合物。螯合二膦配体与双核配合物反应得到Pt_4配合物和Pt_3Pd配合物。这些配合物的分子结构已通过x射线晶体学和详细的核磁共振测量揭示。所得到的配合物有四个Pt(O)或Pd(O)中心与桥接硅烯配体和金属-金属键结合。键长和键角表明配合物具有高度对称的平面结构。配合物的DFT计算表明,四核核心由零价金属中心和中性硅烯配体组成。具有桥接二芳基二甲苯配体的类似钯配合物也被制备和表征。上述反应,形成四核配合物,已被核磁共振波谱跟踪。该反应是由单齿膦配体与螯合的二膦配体交换引起的。随后的双核配合物的缩合伴随着硅基配体转化为硅烯配体或胚基配体转化为二烯配体,从而形成四核配合物。

项目成果

期刊论文数量(17)
专著数量(0)
科研奖励数量(0)
会议论文数量(0)
专利数量(0)
Insertion of Alkynes into the Pt-Si Bond of Silylplatinum Complexes Leading to Formation of 4-Sila- 3-platinacyclobutenes and 5-Sila-2-platina-1,4-cyclohexadienes
将炔烃插入甲硅烷基铂络合物的 Pt-Si 键中,形成 4-Sila-3-铂环丁烯和 5-Sila-2-铂-1,4-环己二烯
Palladium-Platinum Heterobimetallic Complexes with Bridging Silicon Ligands. Structure and Reaction with Isonitrile to Afford a Platinacyclopentane Containing Si, and C Atoms
具有桥接硅配体的钯-铂异双金属配合物。
  • DOI:
  • 发表时间:
    2004
  • 期刊:
  • 影响因子:
    0
  • 作者:
    T.Yamada;M.Tanabe;K.Osakada;Y;Kim
  • 通讯作者:
    Kim
Proparation and Structure of a New Dipalladium Complex with Bridging Dipheylgermyl Ligands. Diverse Reactivities of Pd(PCy_3)_2 and Pt(PCy_3)_2 toward Ph_2GeH_2
具有桥连二苯基甲锗烷基配体的新型二钯络合物的制备和结构。
  • DOI:
  • 发表时间:
    2006
  • 期刊:
  • 影响因子:
    0
  • 作者:
    M.Tanabe;N.Ishikawa;K.Osakada
  • 通讯作者:
    K.Osakada
Theoretical Study of Silyl-Bridged Dinuclear Palladium(I) and Platinum (I) Complexes. M_2(η^2-H SiH_2)_2(PH_3)_2(M=Pd or Pt). New Insight into the Bonding Nature
甲硅烷基桥双核钯(I) 和铂(I) 配合物M_2(η^2-H SiH_2)_2(PH_3)_2(M=Pd 或Pt) 的理论研究。
  • DOI:
  • 发表时间:
    2005
  • 期刊:
  • 影响因子:
    0
  • 作者:
    S.Nakajima;M.Sugimoto;Y.Nakano;H;Sato;S.Sakaki;K.Osakada
  • 通讯作者:
    K.Osakada
Hexanuclear Pt Complexes Composed of Two Cyclic Triplatinum Units Connected with 1,4-Diphenylene and 1,1'-Ferrocenylene Spacer
由两个环状三铂单元与1,4-二亚苯基和1,1-二茂铁间隔基连接组成的六核铂配合物
  • DOI:
  • 发表时间:
    2005
  • 期刊:
  • 影响因子:
    0
  • 作者:
    Masumi Itazaki;Osamu Kitami;Makoto Tanabe;Yasushi Nishihara;Kohtaro Osakada
  • 通讯作者:
    Kohtaro Osakada
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OSAKADA Kohtaro其他文献

OSAKADA Kohtaro的其他文献

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{{ truncateString('OSAKADA Kohtaro', 18)}}的其他基金

Rearrangement of transition metal atom core and structural change and properties change of the framework
过渡金属原子核的重排及骨架的结构变化和性能变化
  • 批准号:
    24350027
  • 财政年份:
    2012
  • 资助金额:
    $ 9.92万
  • 项目类别:
    Grant-in-Aid for Scientific Research (B)
Control of Stereochemistry in Cyclopolymerization of Dienes Using New Symmetrical Palladium Catalyst
使用新型对称钯催化剂控制二烯环聚合的立体化学
  • 批准号:
    23655098
  • 财政年份:
    2011
  • 资助金额:
    $ 9.92万
  • 项目类别:
    Grant-in-Aid for Challenging Exploratory Research
Synthesis and Regulated Functions of Multinuclear Transition Metal Complexes Based on Tetranuclear Palladium and Platinum Complexes
基于四核钯铂配合物的多核过渡金属配合物的合成及功能调控
  • 批准号:
    19205008
  • 财政年份:
    2007
  • 资助金额:
    $ 9.92万
  • 项目类别:
    Grant-in-Aid for Scientific Research (A)
New Reactions of Organmetallic Compounds
有机金属化合物的新反应
  • 批准号:
    11166221
  • 财政年份:
    1999
  • 资助金额:
    $ 9.92万
  • 项目类别:
    Grant-in-Aid for Scientific Research on Priority Areas (A)
Intermolecular transfer of organic ligands among transition metal complexes
过渡金属配合物之间有机配体的分子间转移
  • 批准号:
    09440229
  • 财政年份:
    1997
  • 资助金额:
    $ 9.92万
  • 项目类别:
    Grant-in-Aid for Scientific Research (B)
C-C and C-S bond formlng reactlon uslng nucleophilic Rh and PJ reagents
使用亲核 Rh 和 PJ 试剂的 C-C 和 C-S 键形成反应
  • 批准号:
    04805084
  • 财政年份:
    1992
  • 资助金额:
    $ 9.92万
  • 项目类别:
    Grant-in-Aid for General Scientific Research (C)
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