(1,2-bis(diisopropylphosphino)ethane)Pt(κ2-C,S-C4H4S) | 899832-47-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 噻庚烷
• 英文名称: (1,2-bis(diisopropylphosphino)ethane)Pt(κ2-C,S-C4H4S)
• 英文别名: [(dippe)Pt(η2-C,S-C4H4S)]；(dippe)Pt(κ2-C,S-C4H4S)
• CAS: 899832-47-4
• 化学式: C₁₈H₃₆P₂PtS
• 分子量: 541.577
• InChiKey: BKAFHJAIWVMRBA-LWFKIUJUSA-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：

  2-甲基噻吩 、 (1,2-bis(diisopropylphosphino)ethane)Pt(κ2-C,S-C4H4S) 以 四氢呋喃 为溶剂， 生成 (1,2-bis(diisopropylphosphino)ethane)Pt(SC(CH3)CHCHCH) 、 (dippe)Pt(SCHCHCHC(CH3))
  参考文献：
  名称：

  Predicting Selectivity in Oxidative Addition of C–S Bonds of Substituted Thiophenes to a Platinum(0) Fragment: An Experimental and Theoretical Study

  摘要：

  Exchange reactions of 2- and 3-cyanothiophene, 2- and 3-methylthiophene, and 2- and 3-methoxythiophene, either with thiophene in the thiaplatinacycle Pt(dippe) (kappa(2)-C,S-C4H4S) or with norbornene in Pt(dippe)(nor)(2), were performed to probe the kinetic and thermodynamic selectivity of the C-S bond activation reactions. Kinetic data were collected by following these reactions by P-31{H-1} NMR spectroscopy. The ground-state energies of the two possible products and the transition-state energies leading to the formation of these products were calculated using density functional theory. The comparison of the predicted selectivities from calculations with the experimentally observed selectivities showed good agreement for thermodynamic selectivity, but only moderate agreement for kinetic selectivity. The reactions with 2-cyanothiophene, 3-cyanothiophene, and 3-methoxythiophene gave kinetic products that were less favored thermodynamically. All of the other substituted thiophenes gave kinetic products that were also preferred thermodynamically. These results indicate that the selectivities seen in the C-S bond activation reactions of substituted thiophenes with the [Pt(dippe)] fragment are initially under kinetic control.

  DOI：

  10.1021/om200352d
• 作为产物：
  描述：

  噻吩 、 [Pt(i-Pr2PCH2CH2P-i-Pr2)](μ-η2,η2-cycloocta-1,5-diene) 以 neat (no solvent) 为溶剂， 以80.4%的产率得到(1,2-bis(diisopropylphosphino)ethane)Pt(κ2-C,S-C4H4S)
  参考文献：
  名称：

  The synthesis and structural properties of [M(dippe)(η2-C4H4S)] complexes of Pd and Pt and comparison with their Ni analog

  摘要：

  X-ray structural and NMR spectroscopic data for the ring-opened thiophene complexes [Pd(dippe)(T)] (2), and [Pt(dippe)(T)] (3) are now presented. The complex [Ni(dippe)(T)] (1), where T = (eta(2)-C,S-C4H4S), was reported by our group, previously. The structural and bonding properties of complexes 2 and 3 were compared with those of complex 1. DFT calculations were carried out to rationalize their relative stabilities and structural properties. Compound 1 loses thiophene at ambient temperature in solution, while compound 2 decomposes rapidly in both acetone-d(6) and THF-d(8) with k(obs) = 7.15(9) x 10(-5) and 7.7(3) x 10(-5) s(-1), respectively, to give products that varied by solvent. Complex 3 does not lose thiophene at temperatures below 100 degrees C. The Delta G(0) values determined from DFT calculations are consistent with the observed stabilities of the complexes. The single crystal X-ray structures of all three complexes contain a disordered thienyl fragment in the asymmetric unit due to the interchange of the position of sulfur in the metal-inserted thiophenic ring. The thiophenic moiety is relatively flat in 1, 2 and 3, which is attributed to the open ligand environment at the M(dippe) fragment. All three complexes possess square-planar geometry around the metal center and have bond-length alternation among the thiophenic carbons, which indicates double bond localization. The calculated bond lengths are in good agreement with experimental data. Molecular orbital (MO) and natural bonding orbital (NBO) analyses were carried out to rationalize the results. (c) 2005 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.ica.2005.10.052

文献信息

• Understanding Selectivity in the Oxidative Addition of the Carbon−Sulfur Bonds of 2-Cyanothiophene to Pt(0)
  作者：Tülay A. Ateşin、Abdurrahman Ç. Ateşin、Karlyn Skugrud、William D. Jones

  DOI：10.1021/ic702273a

  日期：2008.6.2

  state energy leading to the formation of the kinetically favored C-S bond cleavage product is lower by 5.3 kcal mol(-1) than the barrier leading to the thermodynamically favored product. There is a 6.7 kcal mol(-1) difference between these two products. The cyano substituent at the 2- position of thiophene did not substantially change the mechanism involved in the C-S bond cleavage of thiophene previously

  2-氰基噻吩与零价铂双烷基膦片段的反应产生两个硫代铂环，其衍生自取代的和未取代的CS键的裂解。尽管在动力学上优选远离氰基的裂解，但在热力学上优选与氰基相邻的裂解。在该系统的模型上使用B3LYP理论水平的密度泛函理论与实验结果一致，导致形成动力学上受支持的CS键裂解产物的过渡态能比势垒低5.3 kcal mol（-1）导致热力学上受青睐的产品。这两种产品之间的差异为6.7 kcal mol（-1）。