cis-[Pt(C6H5)2(P(CH3)3)2] | 343573-63-7

• 分子结构分类: 有机化合物 - 苯类化合物
• 英文名称: cis-[Pt(C6H5)2(P(CH3)3)2]
• 英文别名: cis-[((CH3)3P)2(phenyl)2]
• CAS: 343573-63-7
• 化学式: C₁₈H₂₈P₂Pt
• 分子量: 501.448
• InChiKey: HFRSWUQRJFRXHC-UHFFFAOYSA-N

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：

  cis-[Pt(C6H5)2(P(CH3)3)2] 在 HCl 作用下， 以 乙醚 、 氘代丙酮 为溶剂， 生成 trans-[Pt(C6H5)(CD3)2CO(P(CH3)3)2]BF4
  参考文献：
  名称：

  在中性和阳离子络合物[MR（Cl）{P（CH 3）3 } 2 ]和[MR {P（CH 3）3 ]中，CO插入Pt–C和Pd–C键的过程的实验和理论研究} 2（s）] + BF 4 –（M = Pt，Pd，R = CH 3，C 6 H 5，s =配位溶剂）

  摘要：

  已经检查了中性和阳离子顺-和反-单有机铂络合物的行为，并将其与相应的单有机钯络合物的行为进行了比较。具有两个三甲基膦配体[PtR（丙酮）{P（CH 3）3 } 2 ] + BF 4 –（R = CH 3和C 6 H 5）（4和5）的顺式和反式单有机铂络合物具有通过去除中性络合物[PdR（Cl）{P（CH 3）3 }2 ]（2和3）与一当量的AgBF 4。当在低温下制备时，保留母体中性配合物的顺式构型的阳离子铂配合物被发现异构化为高于-10℃的甲基甲基络合物5a和高于-30℃的苯基络合物异构体的反式络合物5。5b。用CO处理阳离子配合物4和5，没有得到CO插入产物，而仅得到了CO配位的反式。-单有机铂配合物。与相应的有机钯配合物的CO插入的容易性相比，有机铂配合物对CO插入的不耐性得以维持。为了阐明两种10号金属配合物的行为之间存在显着差异的原因，已经进行了从头算分子轨道与MP2能级的计算。

  DOI：

  10.1016/s0022-328x(00)00916-5

文献信息

• Palladium-catalysed formation of aroylcobalt complexes from iodoarene and tetracarbonylcobaltate anion. Syntheses, characterization and reactivities of model intermediate complexes
  作者：Yoshihiko Misumi、Youichi Ishii、Masanobu Hidai

  DOI：10.1039/dt9950003489

  日期：——

  The complex [Pd(PPh(3))(4)] showed good catalytic activity for the formation of aroylcobalt complexes [Co(OCR)(CO)(3)(PPh(3))] from RI (R = aryl), K[Co(CO)(4)] and PPh(3). Attempts to isolate an intermediate Pd-Co complex in this catalytic reaction were unsuccessful, however a series of heterodinuclear complexes [(Ph(3)P)(OC)RPtCo(CO)(3)(PPh(3))] (R = Ph 1a, C(6)H(4)Me-4 1b or Me 1c), [(Me(3)P)(2)(PhCO)PdCo(CO)(4)] 2 and [(Me(3)P)(2)PhPtCo(CO)(4)] 3 have been prepared from reactions of [MR(O3SCF3)(PR'(3))(2)] (M = Pt or Pd, R' = Me or Ph) with K[Co(CO)(4)] as model intermediate complexes. Prior to the formation of complex 1, transient formation of [(Ph(3)P)(2)RPtCo(CO)(4)] was confirmed by P-31 NMR spectroscopy Of the reaction solution. The reaction of [PtPh(O3SCF3)(PMe(3))(2)] with K[Co(CO)(4)] led to the isolation of the corresponding Pt-Co complex 3, while the palladium analogue resulted in the formation of the CO insertion product 2. Crystal structures of compounds 1a, 1c, 2 and 3 were determined by X-ray diffraction analyses. Addition of ligands L such as CO, Bu(t)NC and PMe(3) to 3 in tetrahydrofuran induced heterolytic cleavage of the Pt-Co bond to form [PtPh(PMe(3))(2)L][Co(CO)(4)]. Thermolysis of complexes 1b and 1c under CO at 50 degrees C resulted in reductive elimination of Co(OCC(6)H(4)Me-4)(CO)(3)(PPh(3)) and Co(OCMe)(CO)(3)(PPh(3)), respectively, from the platinum centre. This strongly suggests the involvement of this type of heterodinuclear Pd-Co complex in the catalytic formation of aroylcobalt complexes.