[(dippe)Pd(η2-C,S-C4H4S)] | 899832-46-3

• 分子结构分类: 有机化合物 - 有机盐 - 有机金属盐
• 英文名称: [(dippe)Pd(η2-C,S-C4H4S)]
• 英文别名: (1,2-bis(diisopropylphosphino)ethane)Pd(κ²C,S-thiophene)；(dippe)Pd(κ²C,S-thiophene)
• CAS: 899832-46-3
• 化学式: C₁₈H₃₆P₂PdS
• 分子量: 452.917
• InChiKey: AWRHJMRZCTUMLQ-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：

  [(dippe)Pd(η2-C,S-C4H4S)] 以 氘代四氢呋喃 为溶剂， 生成 (1,2-bis(diisopropylphosphino)ethane)2Pd 、 [Pd(1,2-bis(diisopropylphosphino)ethane)]n
  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
• 作为产物：
  描述：

  噻吩 、 [(1,2-(bis-di-isopropylphosphino)ethane)PdCl2] 在 LiHBEt₃ 作用下， 以 四氢呋喃 为溶剂， 以64.6%的产率得到[(dippe)Pd(η2-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

• Room-Temperature Carbon–Sulfur Bond Activation by a Reactive (dippe)Pd Fragment
  作者：Lloyd Munjanja、William W. Brennessel、William D. Jones

  DOI：10.1021/acs.organomet.5b00194

  日期：2015.5.11

  The reactivity of [Pd(dippe)(μ-H)]2 (1) and [(μ-dippe)Pd]2 (2) (dippe = 1,2-bis(diisopropylphosphino)ethane) toward C–S bonds in thiophene derivatives and thioethers was investigated, which led to C–S bond activation products. The thiapalladacycles derived from thiophenic substrates were fully characterized by 1H, 31P, and 13C NMR spectroscopy, elemental analysis, and X-ray diffraction. The stability

  [Pd（dippe）（μ-H）] 2（1）和[（μ-dippe）Pd] 2（2）（dippe = 1,2-双（二异丙基膦基）乙烷）对C–S键的反应性对噻吩衍生物和硫醚进行了研究，从而得到了CS键活化产物。通过1 H，31 P和13 C NMR光谱，元素分析和X射线衍射对源自噻吩底物的噻吩四环进行了全面表征。的C-S插入产品的稳定性通过进行随后的热力学稳定性顺序（dippe）竞争实验的Pd（κ探测2 Ç，小号苯并噻）（6）>（dippe）的Pd（κ 2 ç，小号-dibenzothiophene）（8）>（dippe）的Pd（κ 2 ç，小号-噻吩）（3）。研究了噻菌四环与小分子（例如H 2，CO和炔烃）的反应性。