Photochemistry of low-valent platinum metal complexes and application to photocatalytic systems

低价铂金属配合物的光化学及其在光催化系统中的应用

基本信息

  • 批准号:
    13640564
  • 负责人:
  • 金额:
    $ 2.24万
  • 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:
    2001
  • 资助国家:
    日本
  • 起止时间:
    2001 至 2003
  • 项目状态:
    已结题

项目摘要

Synthesis of the complexes. [M(triphos)(PPh_3)], [M(binap)_2] (M=Pt and Pd) were synthesized and characterized by elemental analyses and NMR spectroscopy. (triphos = 1,1,1 -tris(diphenylphosphinomethyl)ethane, binap = 1,1' -bis(diphenyl-phosphino)-2,2' -binaphthyl).Analyses of the excited states. The luminescence of [Pd(triphos)(PPh_3)] shows a biexponential decay. The dynamics in the excited state was thoroughly examined.Photochemistry with oxygen. Formation of singlet oxygen is suggested in the initial stage of the photochemical reaction of [Pt(binap)_2] and oxygen. A simple infrared light detection system was constructed, and 1270 nm-light of the emission from singlet oxygen was successfully detected. The singlet oxygen may be formed via an energy-transfer mechanism.Photochemical reaction of the complexes with alcohol. The photochemical reactions of the Pd and Pt complexes with ethanol were, studied. A mercury lamp was used as a light source and, a gas chromatograph was used to identify the organic product in the products. The amounts of the produced acetaldehyde were up to 8 times that of the complex used as a catalyst.Photochemical reaction of the complexes with organic halides. The solution of [M(triphos)(PPh_3)] (or [M(binap)_2]) and 1,2-dichloroethane was irradiated with visible light promptly yielded ethylene quantitatively. In addition, the photochemical dehalogenation of dichloroethane and chlorobenzene by [Pd(triphos) (PPh_3)] catalyst was confirmed with a use of potassium methoxide.
配合物的合成。合成了[M(triphos)(PPh_3)]、[M(binap)_2](M = Pt和Pd),并通过元素分析和NMR进行了表征。(triphos = 1,1,1-三(二苯基膦基甲基)乙烷,binap = 1,1 ′-双(二苯基膦基)-2,2 ′-联萘)。[Pd(triphos)(PPh_3)]的发光呈双指数衰减。在激发态的动力学进行了彻底的检查。光化学与氧。在[Pt(binap)_2]与氧的光化学反应的初始阶段,有单线态氧的生成。构建了一个简单的红外光探测系统,成功地探测到了单线态氧发射的1270 nm光。单重态氧的形成可能是通过能量传递机制。配合物与醇的光化学反应。研究了钯、铂配合物与乙醇的光化学反应。以汞灯为光源,用气相色谱仪鉴定产物中的有机物。乙醛的生成量是配合物催化的8倍以上。配合物与有机卤化物的光化学反应。[M(triphos)(PPh_3)](或[M(binap)_2])与1,2-二氯乙烷的溶液在可见光照射下,迅速定量产生乙烯。此外,还研究了以甲醇钾为催化剂,[Pd(triphos)(PPh_3)]催化二氯乙烷和氯苯的光化学脱卤反应。

项目成果

期刊论文数量(9)
专著数量(0)
科研奖励数量(0)
会议论文数量(0)
专利数量(0)
Z.A.Siddique, T.Ohno, K.Nozaki, T.Tsubomura: "Intense Fluorescence of Metal-to-ligand Charge Transfer in [Pt(0)(binap)_2] [binap=2,2'-bis(diphenylphosphino)-1,1'-binaphthyl]."Inorg.Chem.. 43. 663-673 (2004)
Z.A.Siddique、T.Ohno、K.Nozaki、T.Tsubomura:“[Pt(0)(binap)_2] [binap=2,2-双(二苯基膦)- 中金属到配体电荷转移的强荧光”
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Siddique, Z.A.: "Intense Fluorescence of Metal-to-ligand Charge Transfer in [Pt(0)(binap)_2] [binap=2,2'-bis(diphenylphosphino)-1,1'-binaphthyl."Inorg.Chem.. 43. 663-673 (2004)
Siddique, Z.A.:“[Pt(0)(binap)_2] [binap=2,2-双(二苯基膦)-1,1-联萘基中金属到配体电荷转移的强荧光。”Inorg.Chem
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Tsubomura, T.: "Photophysical and Photochemical Studies of [Pt(binap)_2] ; Excited State Quenching by Oxygen."Bull.Chem.Soc.Jpn.. 76. 2151-2152 (2003)
Tsubomura, T.:“[Pt(binap)_2] 的光物理和光化学研究;氧激发态猝灭。”Bull.Chem.Soc.Jpn.. 76. 2151-2152 (2003)
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Sakai, K.: "(2,2'-Bipyridine)bis(N-methyl-4,4'-bipyridinium) platinum(II) tetraperchlorate"Acta Cryst.. E59. 512-514 (2003)
Sakai,K.:“(2,2-联吡啶)双(N-甲基-4,4-联吡啶鎓)四高氯酸铂(II)”Acta Cryst.. E59。
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T. Tsubomura, T. Tanihata, T. Yamakawa, R. Ohmi, 他4名: "Synthesis and Structure of New Binuclear Organopalladium Macrocyclic Complexes"Organometallics. 20. 3833-3835 (2001)
T. Tsubomura、T. Tanihata、T. Yamakawa、R. Ohmi 和其他 4 人:“新型双核有机钯大环配合物的合成和结构”有机金属学 20. 3833-3835 (2001)
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TSUBOMURA Taro其他文献

TSUBOMURA Taro的其他文献

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{{ truncateString('TSUBOMURA Taro', 18)}}的其他基金

Study on the structure of metal complexes in the excited states by circularly polarized luminescence
圆偏振发光研究激发态金属配合物的结构
  • 批准号:
    21550067
  • 财政年份:
    2009
  • 资助金额:
    $ 2.24万
  • 项目类别:
    Grant-in-Aid for Scientific Research (C)
Structure of d10 metal complexes in the excited states.-For the improvement of emission properties-
激发态的d10金属配合物的结构。-为了提高发射特性-
  • 批准号:
    19550070
  • 财政年份:
    2007
  • 资助金额:
    $ 2.24万
  • 项目类别:
    Grant-in-Aid for Scientific Research (C)
Photochemical reactions and their initial processes of zero-valent metal complexes.
零价金属配合物的光化学反应及其初始过程。
  • 批准号:
    16550060
  • 财政年份:
    2004
  • 资助金额:
    $ 2.24万
  • 项目类别:
    Grant-in-Aid for Scientific Research (C)
The synthesis of the macrocyclic complexes containing low-valent metals.
含有低价金属的大环配合物的合成。
  • 批准号:
    08640723
  • 财政年份:
    1996
  • 资助金额:
    $ 2.24万
  • 项目类别:
    Grant-in-Aid for Scientific Research (C)
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