trans-[ClPt(tri-n-butylphosphine)2(C2C6H4C2C6H5)] | 886972-13-0

• 英文名称: trans-[ClPt(tri-n-butylphosphine)2(C2C6H4C2C6H5)]
• 英文别名: trans-Pt(II)Cl(tributylphosphine)2(CCC6H4CCC6H5)；trans-PtCl(C2(C6H4)C2(C6H5))(PBu3)2
• CAS: 886972-13-0
• 化学式: C₄₀H₆₃ClP₂Pt
• 分子量: 836.421
• InChiKey: SUZZLLPLPAXPDT-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  trans-[ClPt(tri-n-butylphosphine)2(C2C6H4C2C6H5)] 、 1-乙炔-4-((4-(苯基乙炔)苯基)乙炔)苯 在 CuI 作用下， 以 二乙胺 为溶剂， 生成 trans-Pt(II)(tributylphosphine)2(CCC6H4CCC6H5)(CCC6H4CCC6H4CCC6H5)
  参考文献：
  名称：

  Asymmetry in Platinum Acetylide Complexes:  Confinement of the Triplet Exciton to the Lowest Energy Ligand

  摘要：

  To determine structure-optical property relationships in asymmetric platinum acetylide complexes, we synthesized the compounds trans-Pt(PBu3)(2)( C CC6H5)(C C-C6H4-C CC6H5) (PE1-2), trans-Pt(PBu3)(2-)( C CC6H5)(C C-C6H4-C C-C6H4-C CC6H5) (PE1-3) and trans-Pt(PBu3)(2)(C C-C6H4-C CC6H5)( C C-C6H4-C C-C6H4-C CC6H5) (PE2-3) that have different ligands on either side of the platinum and compared their spectroscopic properties to the symmetrical compounds PE1, PE2 and PE3. We measured ground state absorption, fluorescence, phosphorescence and triplet state absorption spectra and performed density functional theory ( DFT) calculations of frontier orbitals, lowest lying singlet states, triplet state geometries and energies. The absorption and emission spectra give evidence the singlet exciton is delocalized across the central platinum atom. The phosphorescence from the asymmetric complexes comes from the largest ligand. Time-dependent (TD) DFT calculations show the S-1 state has mostly highest occupied molecular orbital (HOMO) -> lowest unoccupied molecular orbital (LUMO) character, with the LUMO delocalized over the chromophore. In the asymmetric chromophores, the LUMO resides on the larger ligand, suggesting the S-1 state has interligand charge transfer character. The triplet state geometries obtained from the DFT calculations show distortion on the lowest energy ligand, whereas the other ligand has the ground state geometry. The calculated trend in the triplet state energies agrees very well with the experimental trend. Calculations of triplet state spin density also show the triplet exciton is confined to one ligand. In the asymmetric complexes the spin density is confined to the largest ligand. The results show Kasha's rule applies to these complexes, where the triplet exciton moves to the lowest energy ligand.

  DOI：

  10.1021/jp0654516
• 作为产物：
  描述：

  4-乙炔基二苯乙炔 、 bis(tri-n-butylphosphine)platinum dichloride 在 copper(l) iodide 作用下， 以 二乙胺 为溶剂， 以39%的产率得到trans-[ClPt(tri-n-butylphosphine)2(C2C6H4C2C6H5)]
  参考文献：
  名称：

  一系列具有局部三重态激子的铂乙炔铂配合物的光谱表征。

  摘要：

  在这项工作中，我们描述了一系列铂配合物的光谱性质，该配合物每个铂含一个乙炔配体，化学式为trans-Pt（PBu（3））（2）（（C [三键] CC（6）H （4））（n）（）-H）Cl，n = 1-3（表示为半PEn-Pt），并将其光谱行为与特征明确的系列反式Pt（PBu（3））（2 ）（（C [三键] CC（6）H（4））（n）-H）（2），n = 1-3（指定为PEn-Pt）。该比较旨在确定PEn-Pt的三重态是否局限于一个配体或在整个中心铂原子上离域。我们测量了基态吸收光谱，荧光光谱，磷光光谱和三重态吸收光谱。比较半PEn-Pt和PEn-Pt时，基态吸收光谱和荧光光谱都显示出蓝移，显示S（1）状态在铂上是离域的。相反，两种化合物的磷光光谱具有相同的0-0谱带能，表明T（1）状态局限于PEn-Pt中的一个配体。比较半PEn-Pt和PEn-Pt时，三重态吸收光谱蓝移，表明T（n）状态在

  DOI：

  10.1021/jp056663q

文献信息

• One-Pot Synthesis of <i>trans</i> Mono- or Diarylalkynyl Substituted Platinum(II) Compounds with Tertiary Phosphine or Phosphite Ligands
  作者：Marcus Carlsson、Bertil Eliasson

  DOI：10.1021/om060616i

  日期：2006.10.1

  An efficient one-pot synthesis has been developed for preparation of trans-mono- or diarylalkynyl bisphosphine or bisphosphite Pt(II) compounds. In the procedure, the alkyne and the tertiary phosphorus ligands are mixed with PtCl2 in tetrahydrofuran and triethylamine solution. CuI is added for synthesis of disubstituted complexes, but the catalyst is not used for preparation of monosubstituted complexes

  已经开发了一种有效的一锅合成法，用于制备反式-单-或二芳基炔基双膦或双亚磷酸酯Pt（II）化合物。在该方法中，将炔烃和叔磷配体与PtCl 2在四氢呋喃和三乙胺溶液中混合。加入CuI用于合成双取代的配合物，但是该催化剂不用于制备单取代的配合物。优选使用微波辐射以短时间且高收率得到反式-单-或二芳基炔基Pt（II）化合物。