[Pt(μ-PBu(t)2)(PBu(t)2H)]2 | 322480-55-7

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: [Pt(μ-PBu(t)2)(PBu(t)2H)]2
• CAS: 322480-55-7
• 化学式: C₃₂H₇₄P₄Pt₂
• 分子量: 972.995
• InChiKey: HVYQBHLZSQRPMB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  13.58
• 重原子数：
  38.0
• 可旋转键数：
  2.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  [Pt(μ-PBu(t)2)(PBu(t)2H)]2 以 乙二醇二甲醚 、 甲苯 为溶剂， 生成 [Pt2(μ-PBu(t)2)2(PBu(t)2H)(η(2)-CS2)]
  参考文献：
  名称：

  Dinuclear Phosphido-Bridged Derivatives of Platinum(I). Synthesis and Characterization of [Pt₂(μ-PBu^t₂)₂(PBu^t₂H)(L)] [L = PBu^t₂R (R = H, Li, n-Heptyl), CO, η²-CS₂]

  摘要：

  Contrarily to its palladium analogue, the platinum(II) dihydride [Pt(mu-PBu2t)(H)((PBu2H)-H-t)](2) (3) does not reductively eliminate molecular hydrogen to the corresponding Pt(I) dinuclear derivative. The transformation can, however, be achieved in a two-step procedure, i.e., by oxidant-induced hydride abstraction from 3, which produces the cationic monohydride [Pt-2(mu-PBu2t)(2)(H)((PBu2H)-H-t)(2)]PF6, (4)PF6, and deprotonation of the latter with a strong base, which produces the desired [Pt(mu-PBu2t)((PBu2H)-H-t)](2) (5). Complex 5 can be used as the precursor of other neutral bis-phosphido bridged platinum(I) derivatives. For example, carbon monoxide substitutes in mild conditions one of the terminally bonded secondary phosphines and yields quantitatively the monocarbonyl [Pt-2(mu-PBu2t)(2)((PBu2H)-H-t)(CO)], (6), whose crystal and molecular structure was determined by X-ray diffraction. Crystal data: monoclinic, space group P2(1)/n (No. 14), Z = 4, a = 9.0910(12) Angstrom, b = 30.527(4) Angstrom, c = 11.903(2) Angstrom, beta = 93.78(2)degrees, R(F-o) = 0.0378, Rw(F-o(2)) = 0.0826 [I > 2 sigma(I)]. Complex 6 reacts cleanly with carbon disulfide to give the product of CO substitution [Pt-2(mu-PBu2t)(2)((PBu2H)-H-t)(eta-CS2)] (9) Further modifications of complex 5 can be achieved by deprotonating with n-BuLi/TMEN one of its secondary phosphines, which produces the lithiated derivative [Pt-2(mu-PBu2t)(2)((PBu2H)-H-t)((PBu2Li)-Li-t)] (10). The latter has been alkylated with 1-bromoheptane to the soluble derivative [Pt-2(mu-PBu2t)(2)((PBu2H)-H-t)((PBu2R)-R-t)] (12) (R = n-heptyl).

  DOI：

  10.1021/ic9811392
• 作为产物：
  描述：

  [Pt2(μ-PBu(t)2)2(H)(PBu(t)2H)2]PF6 在 BuLi 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 以64%的产率得到[Pt(μ-PBu(t)2)(PBu(t)2H)]2
  参考文献：
  名称：

  Dinuclear Phosphido-Bridged Derivatives of Platinum(I). Synthesis and Characterization of [Pt₂(μ-PBu^t₂)₂(PBu^t₂H)(L)] [L = PBu^t₂R (R = H, Li, n-Heptyl), CO, η²-CS₂]

  摘要：

  Contrarily to its palladium analogue, the platinum(II) dihydride [Pt(mu-PBu2t)(H)((PBu2H)-H-t)](2) (3) does not reductively eliminate molecular hydrogen to the corresponding Pt(I) dinuclear derivative. The transformation can, however, be achieved in a two-step procedure, i.e., by oxidant-induced hydride abstraction from 3, which produces the cationic monohydride [Pt-2(mu-PBu2t)(2)(H)((PBu2H)-H-t)(2)]PF6, (4)PF6, and deprotonation of the latter with a strong base, which produces the desired [Pt(mu-PBu2t)((PBu2H)-H-t)](2) (5). Complex 5 can be used as the precursor of other neutral bis-phosphido bridged platinum(I) derivatives. For example, carbon monoxide substitutes in mild conditions one of the terminally bonded secondary phosphines and yields quantitatively the monocarbonyl [Pt-2(mu-PBu2t)(2)((PBu2H)-H-t)(CO)], (6), whose crystal and molecular structure was determined by X-ray diffraction. Crystal data: monoclinic, space group P2(1)/n (No. 14), Z = 4, a = 9.0910(12) Angstrom, b = 30.527(4) Angstrom, c = 11.903(2) Angstrom, beta = 93.78(2)degrees, R(F-o) = 0.0378, Rw(F-o(2)) = 0.0826 [I > 2 sigma(I)]. Complex 6 reacts cleanly with carbon disulfide to give the product of CO substitution [Pt-2(mu-PBu2t)(2)((PBu2H)-H-t)(eta-CS2)] (9) Further modifications of complex 5 can be achieved by deprotonating with n-BuLi/TMEN one of its secondary phosphines, which produces the lithiated derivative [Pt-2(mu-PBu2t)(2)((PBu2H)-H-t)((PBu2Li)-Li-t)] (10). The latter has been alkylated with 1-bromoheptane to the soluble derivative [Pt-2(mu-PBu2t)(2)((PBu2H)-H-t)((PBu2R)-R-t)] (12) (R = n-heptyl).

  DOI：

  10.1021/ic9811392

文献信息

• Multinuclear NMR Study and Crystal Structure oftrans-[PtCl2(PHtBu2)2]
  作者：Roberto Giannandrea、Piero Mastrorilli、Mariangela Palma、Francesco Paolo Fanizzi、Ulli Englert、Cosimo Francesco Nobile

  DOI：10.1002/1099-0682(200012)2000:12<2573::aid-ejic2573>3.0.co;2-6

  日期：2000.12

  trans-[PtCl2(PHtBu2)2] (1) was thoroughly characterised by 1H, 31P1H} and 195Pt1H} NMR spectroscopy. Two rotational conformers were found to be stable in solution at room temperature. Force field calculations confirmed that these two conformers are very similar in energy. They co-crystallise in the tetragonal space group P4bar as revealed by X-ray diffraction studies. The dynamics of trans-[PtCl2(PHtBu2)2] is here

  trans-[PtCl2(PHtBu2)2] (1) 通过 1H、31P1H} 和 195Pt1H} NMR 光谱进行了彻底的表征。发现两种旋转构象异构体在室温下在溶液中是稳定的。力场计算证实这两种构象异构体在能量上非常相似。X 射线衍射研究表明，它们在四方空间群 P4bar 中共结晶。此处报道了反式-[PtCl2(PHtBu2)2] 的动力学以及磷桥还原产物的光谱证据。