[Pt(i-Pr2PCH2CH2P-i-Pr2)](μ-η2,η2-cycloocta-1,5-diene) | 202331-12-2

• 英文名称: [Pt(i-Pr2PCH2CH2P-i-Pr2)](μ-η2,η2-cycloocta-1,5-diene)
• 英文别名: [((dippe)Pt)2(μ-η2, η2-cyclooctadiene)]
• CAS: 202331-12-2
• 化学式: C₃₆H₇₆P₄Pt₂
• 分子量: 1023.05
• InChiKey: YUDFWEHWQGOMBD-JXNOXZOESA-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：

  [Pt(i-Pr2PCH2CH2P-i-Pr2)](μ-η2,η2-cycloocta-1,5-diene) 、 1,5-环辛二烯 以 氘代四氢呋喃 为溶剂， 生成
  参考文献：
  名称：

  Novel (R₂PC₂H₄PR₂)M⁰−COT Complexes (M = Pd, Pt) Having Semiaromatic η²-COT or Dianionic η²(1,4)-COT Ligands

  摘要：

  The complexes (R2PC2H4PR2)Pd(C2H4) (R = Pr-i, Bu-t) react with COT by displacement of the ethene ligand to afford the novel mononuclear complexes (R2PC2H4PR2)Pd(eta(2)-C8H8) (R = Pr-i (1a), tBu (1b)). The COT ligand of 1a,b is semiaromatic; i.e., it is planar with alternating C-C and C=C bonds as expected for the monoanion [C8H8](-). Treatment of 1a,b with (R2PC2H4PR2)Pd-alkene complexes generates the dinuclear derivatives {(R2PC2H4PR2)Pd}(2)(mu-eta(2),eta(2)-C8H8) (R = Pr-i (2a), Bu-t(2b)). The complexes 2a,b are labile; elimination of the COT ligand from 2a gives rise to homoleptic Pd-2(mu-d(i)ppe)(2). Reaction of (d(i)ppe)PtCl2 with (tmeda)(2)Li2COT or displacement of the alkene ligands in {(d(i)ppe)Pt}a(mu-eta(2),eta(2)-C8H12) (4) or (d(i)ppe)Pt(C2H4) (5) by COT produces (d(i)ppe)Pt(eta(2)-C8H8) (6a), which in the solid state also has a semiaromatic COT ligand. In solution, complex 6a is in equilibrium with the novel isomeric form (d(i)ppe)Pt-II{eta(2)(1,4)-C8H8} (6b). The complexes are characterized by IR, MS, and solution and solid-state NMR.

  DOI：

  10.1021/om970762b
• 作为产物：
  描述：

  1,2-双(二-异丙基膦基)乙烷 、 bis(cycloocta-1,5-diene)platinum(0) 以 乙醚 为溶剂， 以50%的产率得到[Pt(i-Pr2PCH2CH2P-i-Pr2)](μ-η2,η2-cycloocta-1,5-diene)
  参考文献：
  名称：

  Novel (R₂PC₂H₄PR₂)M⁰−COT Complexes (M = Pd, Pt) Having Semiaromatic η²-COT or Dianionic η²(1,4)-COT Ligands

  摘要：

  The complexes (R2PC2H4PR2)Pd(C2H4) (R = Pr-i, Bu-t) react with COT by displacement of the ethene ligand to afford the novel mononuclear complexes (R2PC2H4PR2)Pd(eta(2)-C8H8) (R = Pr-i (1a), tBu (1b)). The COT ligand of 1a,b is semiaromatic; i.e., it is planar with alternating C-C and C=C bonds as expected for the monoanion [C8H8](-). Treatment of 1a,b with (R2PC2H4PR2)Pd-alkene complexes generates the dinuclear derivatives {(R2PC2H4PR2)Pd}(2)(mu-eta(2),eta(2)-C8H8) (R = Pr-i (2a), Bu-t(2b)). The complexes 2a,b are labile; elimination of the COT ligand from 2a gives rise to homoleptic Pd-2(mu-d(i)ppe)(2). Reaction of (d(i)ppe)PtCl2 with (tmeda)(2)Li2COT or displacement of the alkene ligands in {(d(i)ppe)Pt}a(mu-eta(2),eta(2)-C8H12) (4) or (d(i)ppe)Pt(C2H4) (5) by COT produces (d(i)ppe)Pt(eta(2)-C8H8) (6a), which in the solid state also has a semiaromatic COT ligand. In solution, complex 6a is in equilibrium with the novel isomeric form (d(i)ppe)Pt-II{eta(2)(1,4)-C8H8} (6b). The complexes are characterized by IR, MS, and solution and solid-state NMR.

  DOI：

  10.1021/om970762b

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）。
• The synthesis and structural properties of [M(dippe)(η2-C4H4S)] complexes of Pd and Pt and comparison with their Ni analog
  作者：Tülay A. Ateşin、Stephen S. Oster、Karlyn Skugrud、William D. Jones

  DOI：10.1016/j.ica.2005.10.052

  日期：2006.6

  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.