[(depe)PtCl₂] | 15630-13-4

• 分子结构分类: 有机化合物 - 有机杂环化合物
• 英文名称: [(depe)PtCl₂]
• 英文别名: Cl₂Pt(II)(depe)；Cl₂Pt(II)(1,2-bis(diethylphosphino)ethane)；1,2-bis(diethylphosphino)ethane platinum(II) dichloride；cis-Pt(1,2-bis(diethylphosphino)ethane)Cl2；[PtCl2(1,2-bis(diethylphosphino)ethane)]；[PtCl2(depe)]；2-diethylphosphanylethyl(diethyl)phosphane;platinum(2+);dichloride
• CAS: 15630-13-4
• 化学式: C₁₀H₂₄Cl₂P₂Pt
• 分子量: 472.234
• InChiKey: QXHGAAULXGOQAN-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  -1.96
• 重原子数：
  15
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  [(depe)PtCl₂] 、 biphenyl-2,2'-diyl-bis-lithium 以 苯 为溶剂， 以70%的产率得到(bis(diethylphosphino)ethane)Pt(2,2'-biphenyl)
  参考文献：
  名称：

  铂钯膦配合物催化碳-碳键活化和形成的机理研究

  摘要：

  配合物 Pt(PEt3)3 和 Pd(PEt3)3 裂解联苯的 C-C 键，得到 (PEt3)2Pt(2,2'-联苯), 1, 和 (PEt3)2Pd(2,2'-联苯) ）， 分别。在亚联苯存在下加热 (PEt3)2Pt(2,2'-联苯) 导致第二个亚联苯的 C-C 裂解得到 (PEt3)2Pt(2,2'-四苯基), 2，通过 Pt(IV) ） 中间的。2 在 115 °C 时还原消除四亚苯基。在 120 °C 时，反应是催化的；Pt(PEt3)3 或 1 将亚联苯转化为四亚苯基。催化循环中的中间体已被鉴定，1 和 2 已通过 X 射线分析表征。在催化条件下，1 和 2 接近稳态浓度。动力学分析表明，稳态浓度比、静止状态种类和总催化速率 kobs 取决于联苯与 PEt3 的比率。

  DOI：

  10.1021/ja973368d
• 作为产物：
  描述：

  dichloro( 1,5-cyclooctadiene)platinum(ll) 、 1,2-双(二乙基磷)乙烷 以 二氯甲烷 为溶剂， 以60%的产率得到[(depe)PtCl₂]
  参考文献：
  名称：

  Equilibria between Metallosupramolecular Squares and Triangles with the New Rigid Linker 1,4-Bis(4-pyridyl)tetrafluorobenzene. Experimental and Theoretical Study of the Structural Dependence of NMR Data

  摘要：

  The new fluorinated rigid ligand L, 1,4-bis(4-pyridyl)tetrafluorobenzene, was used in combination with different diphosphine Pd(II) and Pt(II) triflates to build metallosupramolecular assemblies. Complex equilibria between triangular and square entities were detected for all the cases. Characterization of the equilibria was accomplished by H-1, P-31{H-1}, F-19, and Pt-195{H-1} NMR in combination with mass spectrometry. The square/triangle ratio was seen to depend on several factors, such as the nature of the metal corners, the concentration, and the solvent. The relative stability of the square and triangular complexes was explored by using force field methods. A GIAO-DFT study was carried out to analyze the changes of the P-31 and H-1 NMR data with the geometry of the complexes.

  DOI：

  10.1021/ic034489j

文献信息

• Steric Effects in the Baeyer−Villiger Oxidation of Ketones Catalyzed by Platinum(II) Lewis Acid Complexes with Coordinated Electron-Donor Alkyl Diphosphines
  作者：Paolo Sgarbossa、Alessandro Scarso、Rino A. Michelin、Giorgio Strukul

  DOI：10.1021/om070077x

  日期：2007.5.1

  complexes were tested in the Baeyer−Villiger oxidation of 2-methylcyclohexanone, 2-methylcyclopentanone, and cyclobutanone with 35% hydrogen peroxide as oxidant. The reactions were performed at 20 and 70 °C in a chlorinated solvent/H2O two-phase system. Within the above-reported series of complexes, 1e gave the highest catalytic activity and productivity in the oxidation of cyclic ketones. The Lewis

  [Pt（μ-OH）（P-P）] 2 [BF 4 ] 2（1a - d）类型的新型羟基桥联铂（II）配合物的合成与表征，其中PP = R 2 PCH 2 CH 2 PR 2（R = Me，dmpe，1a ; Et，depe，1b ; i -Pr，dippe，1c ; Cy，dcype，1d）和[Pt（P-P）（H 2 O）2 ] [BF 4 ] 2）（其中R = t -Bu，dtbpe，1e）的报告。这些配合物在2-甲基环己酮，2-甲基环戊酮和环丁酮的Baeyer-Villiger氧化反应中用35％的过氧化氢作为氧化剂进行了测试。反应在20和70°C的氯化溶剂/ H 2 O两相系统中进行。在上述报告的一系列配合物中，1e在环酮的氧化反应中具有最高的催化活性和生产率。通过确定[PtCl（CN-2,6）型配合物中不含异氰酸酯部分的波数位移Δν̄=ν̄（C⋮N）坐标-ν̄（C⋮N），研究了1a -
• Reactivity of 1-alkynylplatinum(II) complexes towards trialkylboranes
  作者：Bernd Wrackmeyer、Angelika Sebald

  DOI：10.1016/s0022-328x(97)00319-7

  日期：1997.10

  of a PtC bond, and formation of an alkynylborate-like intermediate in which a positively charged platinum fragment is coordinated to the CC bond. In most cases, the alkenylplatinum complexes of the type 9–13, 28, 30 which result from 1,1-organoboration are not stable, and either η2-alkyne platinum(0) (15–21, 29) or η3-borylalene platinum(0) complexe (22–27) or both are the next products. The proposed

  1-Alkynylplatinum（II）的类型的复合物的顺式- [（DPPE）的Pt（CCR 1 2 ] [ 4，R 1 我（一），BU（b）中，C（Me）的CH 2（ e），Ph（d），SiMe 3（e）]顺式-[（dmpe）Pt（CCMe）2 ]（5a），顺式-[（depe）Pt（CCPh）2 ] （图6d），顺式- [（ET 3 P）2铂（“卜）（CCR 1）] [ 7：R 1 我（一个。）PH（d）和反式-[（（Et 3 P）2 Pt（（E）-2-戊烯基）（CC-Me）]（8a）与三烷基硼烷R 3 B [2，RMe（a），Et（b），Pr（c）]通过1,1-有机合成。这涉及到PtC键的裂解，以及形成炔基硼酸酯样中间体，其中带正电的铂片段与CC键配位。在大多数情况下，该类型的复合物alkenylplatinum 9-13，28，30从1,1- org
• Platinum(II) Acetylides in the Formal [2+2] Cycloaddition-Retroelectrocyclization Reaction: Organodonor Versus Metal Activation
  作者：Boris H. Tchitchanov、Melanie Chiu、Markus Jordan、Milan Kivala、W. Bernd Schweizer、François Diederich

  DOI：10.1002/ejoc.201300300

  日期：2013.6

  Formal cycloaddition-retroelectrocyclization (CA-RE) reactions between electron-donor-activated alkynes and electron-poor alkenes yielding cyanobuta-1,3-dienes have recently attracted increasing interest. The transformation has been subjected to a fundamental investigation of the relative degrees of alkyne activation by organic and metallorganic donor substituents by using platinum(II) σ-acetylides

  电子供体活化的炔烃和缺电子烯烃之间的正式环加成 - 逆电环化（CA-RE）反应最近引起了越来越多的兴趣。通过使用铂 (II) σ-炔化物作为模型底物并研究它们对氰基碳 TCNE 和 TCNQ 的行为，对有机和金属有机供体取代基对炔烃活化的相对程度进行了基本研究。各种氰基丁二烯都以良好到极好的收率获得，并且发现了四种反应性趋势：1) 苯胺基取代基的存在明显支配了 TCNQ 添加的区域选择性。2) 在没有有机供体的情况下，区域选择性被反转。3) 当使用buta-1,3-diynes的铂(II)配合物时，添加总是发生在远离金属中心的三键处。4) 一般来说，反式双乙炔化合物比相应的顺式配合物更具反应性。通过 X 射线晶体学研究 CA-RE 加合物的结构参数，并通过紫外/可见光谱研究它们的光学性质，进一步了解分子内电荷转移的结构趋势和程度。这些基础研究可能有助于合成新的基于 Pt 的分子二元组，其中
• Synthesis and optical properties of chlorophyll dimers bridged by cis- and trans-forms of Pt(II) bis-acetylide complexes
  作者：Youhei Yamamoto、Hitoshi Tamiaki

  DOI：10.1016/j.jorganchem.2013.10.036

  日期：2014.1

  dimers, cis- and trans-forms 1 and 2 connected by a platinum(II) bis-acetylide complex were synthesized by copper(I)-catalyzed coupling of a monomeric Zn–Chl derivative possessing an ethynyl group at the C3 position 5 with the cis- and trans-isomers of Pt(II) bisphosphine complexes, respectively. The corresponding cis- and trans-forms of Zn–Chl monomers 3 and 4 bonding a phenyl group through Pt(II) bis-acetylide

  两种异构锌叶绿素（ZN-CHL）二聚体，顺式-和反式-forms 1和2的铂（II）双连接乙炔化物络合物，通过合成铜（I）催化的单体的Zn-CHL的耦合衍生物具有在C3位5的乙炔基分别具有Pt（II）双膦配合物的顺式和反式异构体。还制备了通过Pt（II）双-乙炔键与苯基键合的Zn-Chl单体3和4的相应的顺式和反式形式。这些合成配合物的特征为11 H NMR，IR和MS光谱。可见吸收和圆二色光谱1 - 5在有机溶剂中进行测定，显示出redmost（QY）的条带1和2被转移到比那些更长的波长3和4分别。红移归因于二氢卟酚环中π共轭通过Pt（II）连接单元沿分子y轴的延伸。与相应的顺式异构体1和3相比，反式二聚体2和单体4的Qy最大值发生红移。红移是由于反式Pt复合物中的π共轭比顺式异构体更大。
• Platinum(II) diphosphine complexes as catalysts for the Baeyer–Villiger oxidation of ketones: Is it possible to increase the concentration of the active species?
  作者：Gilberto Greggio、Paolo Sgarbossa、Alessandro Scarso、Rino A. Michelin、Giorgio Strukul

  DOI：10.1016/j.ica.2007.10.042

  日期：2008.7

  The synthesis and characterization of new bis-aquo platinum(II) complexes of the type [Pt(H2O)(P-P)][OTf](2) (OTf = triflate anion), in which the diphosphine P-P is a series of 1,n-bis-diphenyphosphinoalkanes (1a-d, with n = 1-4), 1,2-bis-(di-n-fluorophenylphosphino) ethanes (2a-c, with n = 2, 4-5) and 1,2-bis-dialkylphosphinoethanes (3a-e), where the alkyl substituents at phosphorus have been systematically changed (dmpe) (3a), (depe) (3b), (dippe) (3c), (dcype) (3d) are reported. These complexes were used as catalysts in the Baeyer-Villiger oxidation of 2-methylcyclohexanone, 2-methylcyclopentanone and cyclobutanone with 35% hydrogen peroxide as an environmentally friendly oxidant. The reactions were performed at 25 degrees C in a chlorinated solvent/H2O two-phase system. All the investigated catalysts performed better than the corresponding dimeric complexes of general formula [Pt(mu-OH)(P-P)](2)[BF4](2) as a consequence of the positive effect imparted by the triflate counter-anion on catalysts speciation. (C) 2007 Elsevier B.V. All rights reserved.