bridge-Pt4(CH3COO)4((C2H5O)2PS2)4 | 253191-64-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: bridge-Pt4(CH3COO)4((C2H5O)2PS2)4
• CAS: 253191-64-9；253191-65-0
• 化学式: C₂₄H₅₂O₁₆P₄Pt₄S₈
• 分子量: 1757.41
• InChiKey: PAMRZMSULPDXCY-UHFFFAOYSA-F

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：

  bridge-Pt4(CH3COO)4((C2H5O)2PS2)4 以 氘代乙腈 为溶剂， 生成 chelate-Pt4(CH3COO)4((C2H5O)2PS2)4
  参考文献：
  名称：

  Syntheses and Structures of Bridge and Chelate Isomers of Tetraplatinum(II) Cluster Complex with Diethyldithiophosphate Ion (Et₂dtp) at In-Plane Sites, [Pt₄(CH₃COO)₄(Et₂dtp)₄], and Their Mutual Isomerization via Cluster Core Rotation

  摘要：

  A reaction of [Pt-4(CH3COO)(8)], with an excess of diethyldithiophosphate (Et(2)dtpH) in CH3CN affords a tetrasubstituted derivative, [Pt-4(CH3COO)(4)(Et(2)dtp)(4)], which is a mixture of two isomers. X-ray analyses of the isolated two isomers revealed that Et(2)dtp ligands in both isomers are coordinated in the plane of the Pt-4 cluster core, and that coordination mode of Et(2)dtp is the chelate type in one isomer (2) whereas it is the bridge type in the other (3)H-1 NMR studies showed that both 2 and 3 isomerize slowly in solution to give the same equilibrium mixture. The rate constants for the isomerization in CDCl3 at 40 degrees C were k(1) = 1.2 x 10(-4) s(-1) (for the reaction from 2 to 3) and k(2) = 1.5 x 10(-4) s(-1) (for the reaction from 3 to 2), respectively. Both 2 and 3 undergo the isomerization also in acetonitrile with similar reaction rate, but the mechanism is different from that in chloroform. Activation entropy for the reaction starting from 2 to 3 was -9 +/- 9 J mol(-1) K-1 in chloroform and -47 +/- 11 J mol(-1) K-1 in acetonitrile. The small \Delta S-double dagger\ value for the reaction in chloroform suggests that the isomerization proceeds without bond cleavage through an intermediate when three sulfur atoms from two Et(2)dtp's are coordinated to each platinum. That is, the isomerization in chloroform is caused by rotation of the Pt cluster core within an array of eight S atoms arranged circularly in a single plane. On the other hand, the isomerization in acetonitrile proceeds via a Pt-S bond cleaved intermediate possibly by the solvent assisted mechanism. All the kinetic parameters for the reactions in CDCl3 and CD3CN are reported.

  DOI：

  10.1021/ja990596u
• 作为产物：
  描述：

  chelate-Pt4(CH3COO)4((C2H5O)2PS2)4 以 氘代氯仿 、 水 为溶剂， 生成 bridge-Pt4(CH3COO)4((C2H5O)2PS2)4
  参考文献：
  名称：

  Syntheses and Structures of Bridge and Chelate Isomers of Tetraplatinum(II) Cluster Complex with Diethyldithiophosphate Ion (Et₂dtp) at In-Plane Sites, [Pt₄(CH₃COO)₄(Et₂dtp)₄], and Their Mutual Isomerization via Cluster Core Rotation

  摘要：

  A reaction of [Pt-4(CH3COO)(8)], with an excess of diethyldithiophosphate (Et(2)dtpH) in CH3CN affords a tetrasubstituted derivative, [Pt-4(CH3COO)(4)(Et(2)dtp)(4)], which is a mixture of two isomers. X-ray analyses of the isolated two isomers revealed that Et(2)dtp ligands in both isomers are coordinated in the plane of the Pt-4 cluster core, and that coordination mode of Et(2)dtp is the chelate type in one isomer (2) whereas it is the bridge type in the other (3)H-1 NMR studies showed that both 2 and 3 isomerize slowly in solution to give the same equilibrium mixture. The rate constants for the isomerization in CDCl3 at 40 degrees C were k(1) = 1.2 x 10(-4) s(-1) (for the reaction from 2 to 3) and k(2) = 1.5 x 10(-4) s(-1) (for the reaction from 3 to 2), respectively. Both 2 and 3 undergo the isomerization also in acetonitrile with similar reaction rate, but the mechanism is different from that in chloroform. Activation entropy for the reaction starting from 2 to 3 was -9 +/- 9 J mol(-1) K-1 in chloroform and -47 +/- 11 J mol(-1) K-1 in acetonitrile. The small \Delta S-double dagger\ value for the reaction in chloroform suggests that the isomerization proceeds without bond cleavage through an intermediate when three sulfur atoms from two Et(2)dtp's are coordinated to each platinum. That is, the isomerization in chloroform is caused by rotation of the Pt cluster core within an array of eight S atoms arranged circularly in a single plane. On the other hand, the isomerization in acetonitrile proceeds via a Pt-S bond cleaved intermediate possibly by the solvent assisted mechanism. All the kinetic parameters for the reactions in CDCl3 and CD3CN are reported.

  DOI：

  10.1021/ja990596u