cis-dichlorobis(dicyclohexylphosphane)platinum(II) | 122700-83-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: cis-dichlorobis(dicyclohexylphosphane)platinum(II)
• 英文别名: cis-{PtCl2(PCy2H)2}；cis-PtCl₂(PHCy₂)₂；cis-[PtCl2(PHCy2)2]；cis-[PtCl2(PHCy)2]
• CAS: 122700-83-8
• 化学式: C₂₄H₄₆Cl₂P₂Pt
• 分子量: 662.563
• InChiKey: MSLSYPYUAYATGO-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  10.04
• 重原子数：
  29.0
• 可旋转键数：
  6.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  cis-dichlorobis(dicyclohexylphosphane)platinum(II) 在 NaOH 作用下， 以 二氯甲烷 、 水 、 丙酮 、 甲苯 为溶剂， 生成 syn-[(PHCy2)(κP-O(O)Cy2)Pt(μ-PCy2)(μ-H)Pt(PHCy2)(κP-P(O)Cy2)]*2H2O
  参考文献：
  名称：

  Reactivity of a Phosphinito-Bridged Pt^I−Pt^I Complex with Nucleophiles: Substitution versus Addition

  摘要：

  As a result of the strong electrophilic character of the Pt bound to O, the phosphinito-bridged Pt-I complex [(PHCy2)Pt(mu-PCy2){kappa P-2, O-mu-P(O)Cy-2}Pt(PHCy2)](Pt-Pt) (1) undergoes attack at the O-bound Pt atom by molecules such as di- and tricyclohexylphosphane, dicyclohexylphosphane oxide, and dicyclohexylphosphane sulfide. Thus, reaction of 1 with PHCy2 gives the symmetric Pt-I dimer [(PHCy2)Pt(mu-PCy2)](2)(Pt-Pt) (2), while the hydrido-bridged complex syn-[(PHCy2)[kappa P-P(O)Cy-2[Pt(mu-PCy2)(mu-H)Pt(PHCy2){kappa P-P(O)Cy-2}](Pt-Pt) (4) is obtained from reaction of 1 with P(O)HCy2; the thiophosphinito complex [(PHCy2)Pt(mu-PCy2){kappa P-2,S-mu-P(S)Cy-2}Pt(PHCy2)](Pt-Pt) (8) forms selectively in reaction of 1 with P(S)HCy2. For comparison, the reaction with PCy3 results only in ligand substitution, affording [(PCy3)Pt(mu-PCy2){kappa P-2,O-mu-P(O)Cy-2)Pt(PHCy2)](Pt-Pt) (5). DFT studies confirmed the remarkable electrophilicity of the oxygen-bound Pt and shed light on the nature of the metal-metal bond in Pt dimers.

  DOI：

  10.1021/ic800045u
• 作为产物：
  描述：

  二环己基膦 、 trans-bis(benzonitrile)dichloroplatinum(II) 以 甲苯 为溶剂， 以85%的产率得到cis-dichlorobis(dicyclohexylphosphane)platinum(II)
  参考文献：
  名称：

  (Phosphido)platinum Complexes by Sodium-Promoted Reaction ofcis-PtCl2(PHCy2)2 − Synthesis and Crystal Structure of [trans-Pt(PCy2H)2(PCy2)Cl], a Rare Example of a Terminal (Phosphido)platinum(II) Complex

  摘要：

  DOI：

  10.1002/1099-0682(200205)2002:5<1210::aid-ejic1210>3.0.co;2-3

文献信息

• Stepwise Sulfuration of the Terminal Phosphido Complex <i>trans</i> ‐[PtCl(PHCy ₂ ) ₂ (PCy ₂ )]: Synthesis of [Pt(κ ² <i>S</i> , <i>S′</i> ‐PS ₂ Cy ₂ )(PHCy ₂ ) ₂ ]Cl and [Pt(κ ² <i>S</i> , <i>S′</i> ‐PS ₂ Cy ₂ ){κ <i>P</i> ‐P(S)Cy ₂ }(PHCy ₂ )] and Crystal Structure of [Pt(κ ² ‐ <i>S</i> , <i>S</i> ‐PCy ₂ S ₂ )(κ‐ <i>S</i> ‐PCy ₂ S ₂ )(PHCy ₂ )]
  作者：Vito Gallo、Mario Latronico、Piero Mastrorilli、Cosimo Francesco Nobile、Giuseppe Ciccarella、Ulli Englert

  DOI：10.1002/ejic.200600174

  日期：2006.7

  solvents into cis-[PtCl(PHCy2)2κP-P(S)Cy2}] (3). Further addition of sulfur causes the formation of a mixture of [Pt(κ2S,S′-PS2Cy2)(PHCy2)2]Cl (4) and [Pt(κ2S,S′-PS2Cy2)κP-P(S)Cy2}(PHCy2)] (5), which could be selectively synthesised; the first upon sulfuration of pure 3 and the second by reaction of 4 with 1 equiv. of sulfur in the presence of DBU. Complex 5 can be further sulfurated to [Pt(κ2S,S′-PCy2

  通过 1,8-二氮杂双环 [5.4.0] undec-7-ene 的作用，利用与 HCl 反应的可逆性，制备了末端磷基复合物反式-[PtCl(PHCy2)2(PCy2)] (1) (DBU) 在 [PtCl(PHCy2)3]Cl 上，及其对元素硫的反应性研究。1与1当量反应得到的第一个产物。硫的反式-[PtCl(PHCy2)2κP-P(S)Cy2}] (2)，它在卤化溶剂中迅速异构化成顺式-[PtCl(PHCy2)2κP-P(S)Cy2}] (3). 进一步添加硫会导致形成 [Pt(κ2S,S'-PS2Cy2)(PHCy2)2]Cl (4) 和 [Pt(κ2S,S'-PS2Cy2)κP-P(S)Cy2} 的混合物(PHCy2)] (5)，可选择性合成；第一个是纯 3 的硫化，第二个是 4 与 1 当量的反应。在 DBU 存在下的硫。配合物 5 可以进一步硫化成 [Pt(κ2S,S'-
• Synthesis of Phosphido‐Bridged Phosphinito Platinum( <scp>I</scp> ) Complexes by Reaction of <i>cis</i> ‐PtCl ₂ (PHCy ₂ ) ₂ with Oxygenated Bases – Crystal Structure of [(PCy ₂ OMe)Pt(μ‐PCy ₂ )] ₂ ( <i>Pt</i> – <i>Pt</i> )
  作者：Vito Gallo、Mario Latronico、Piero Mastrorilli、Cosimo F. Nobile、Gian P. Suranna、Giuseppe Ciccarella、Ulli Englert

  DOI：10.1002/ejic.200500510

  日期：2005.11

  phosphido-bridged dinuclear complexes. The product obtained using sodium hydroxide is the asymmetric PtI complex [(Cy2PH)Pt(μ-PCy2)(κ2P,O-μ-Cy2PO)Pt(Cy2PH)](Pt–Pt) (2), which represents a rare example of a complex containing a Pt–Pt–P–O cycle. The reaction products between 1 and NaOR (R = Me, Et) depend on experimental conditions: lack of base results in the formation of trans-[Pt(PHCy2)Cl(μ-PCy2)]2 (3)

  cis-PtCl2(PHCy2)2 (1) 与含氧碱基反应生成磷桥双核复合物。使用氢氧化钠获得的产物是不对称 PtI 复合物 [(Cy2PH)Pt(μ-PCy2)(κ2P,O-μ-Cy2PO)Pt(Cy2PH)](Pt-Pt) (2)，它代表了一个罕见的例子包含 Pt-Pt-P-O 循环的复合物。1 和 NaOR (R = Me, Et) 之间的反应产物取决于实验条件：缺乏碱会导致形成反式-[Pt(PHCy2)Cl(μ-PCy2)]2 (3) 作为主要产物。在 50 °C 下使用过量的碱可以分离对称 PtI 二聚体 [(PCy2OR)Pt(μ-PCy2)]2(Pt–Pt) (5, R = Me; 7, R = Et) 包含两个烷基二环己基膦配体。不对称化合物 [(PCy2H)Pt(μ-PCy2)2Pt(PCy2OR)](Pt–Pt) (4, R = Me; 8, R = Et) 在 1 与过量
• Multinuclear and Dynamic NMR Study of <i>trans</i>-[Pt(Cl)(PHCy₂)₂(PCy₂)], [Pt(Cl)(PHCy₂)₃][BF₄], [Pt(Cl)(PHCy₂)₃][Cl], <i>trans</i>-[Pt(Cl)(PHCy₂)₂{P(S)Cy₂}], and <i>trans</i>-[Pt(Cl)(PHCy₂)₂{P(O)Cy₂}]. Influence of Intramolecular PO···H−P and Cl···H−P Interactions on Restricted Rotation about Pt−P Bond. X-ray Structure of <i>trans</i>-[Pt(Cl)(PHCy₂)₂{P(O)Cy₂}]
  作者：Piero Mastrorilli、Cosimo F. Nobile、Mario Latronico、Vito Gallo、Ulli Englert、Francesco P. Fanizzi、Oronzo Sciacovelli

  DOI：10.1021/ic051198x

  日期：2005.11.1

  NMR experiments on trans-[Pt(Cl)(PHCy2)2[P(X)Cy2]]z where X is a lone pair (1, z = 0), H (2, z = +1), S (3, z = 0), or O (4, z = 0) show that the rotation around the P(X)-Pt bond is hindered for all molecules studied, with deltaG++ ranging from 8.2 to 11.0 kcal/mol. The highest value of the series was calculated for trans-[Pt(Cl)(PHCy2)2[P(O)Cy2]] (4) where intramolecular P=O...H-P interactions act

  反式-[Pt（Cl）（PHCy2）2 [P（X）Cy2]] z的动态NMR实验，其中X为孤对（1，z = 0），H（2，z = +1），S（ 3，z = 0）或O（4，z = 0）表明，对于所有研究的分子，围绕P（X）-Pt键的旋转均受阻，deltaG ++的范围为8.2至11.0 kcal / mol。该系列的最高值是针对反式-[Pt（Cl）（PHCy2）2 [P（O）Cy2]]（4）计算的，其中分子内P = O ... HP相互作用在室温下起分子制动作用。X射线单晶衍射证实固体4中存在分子内和分子间P = O ... H相互作用。在[Pt（Cl）（PHCy2）3] Cl的情况下，多核NMR分析表明存在在芳香族或卤代溶剂中的PH ... Cl-相互作用也可能对P（X）-Pt键周围的旋转势垒产生较小影响。
• Blum, Thierry; Braunstein, Pierre; Tiripicchio, Antonio, Organometallics, 1989, vol. 8, # 11, p. 2504 - 2513
  作者：Blum, Thierry、Braunstein, Pierre、Tiripicchio, Antonio、Camellini, Marisa Tiripicchio

  DOI：——

  日期：——