trans-bis(tri-tert-butylphosphine)platinum(II) dihydride | 67870-05-7

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: trans-bis(tri-tert-butylphosphine)platinum(II) dihydride
• 英文别名: trans-H₂Pt(P^tBu₃)₂；trans-[PtH2(P(t)Bu3)2]；platinum dihydride;tritert-butylphosphane
• CAS: 67870-05-7；1013923-81-3
• 化学式: C₂₄H₅₆P₂Pt
• 分子量: 601.736
• InChiKey: BHRJPSVCSIRZKY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.19
• 重原子数：
  27.0
• 可旋转键数：
  2.0
• 环数：
  0.0
• 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：

  trans-bis(tri-tert-butylphosphine)platinum(II) dihydride 在 碘 作用下， 以 苯 为溶剂， 生成 bis(tri-tert-butyl-l⁵-phosphanyl)platinum(IV) hydride iodide
  参考文献：
  名称：

  Goel, Ram G.; Oginl, William O.; Srivastava, Ramesh C., Organometallics, 1982, vol. 1, # 6, p. 819 - 824

  摘要：

  DOI：
• 作为产物：
  描述：

  trans-bis(tri-tert-butylphosphine)chlorohydridoplatinum(II) 在 sodium tetrahydroborate 作用下， 以 四氢呋喃 为溶剂， 以90%的产率得到trans-bis(tri-tert-butylphosphine)platinum(II) dihydride
  参考文献：
  名称：

  Goel, Ram G.; Oginl, William O.; Srivastava, Ramesh C., Organometallics, 1982, vol. 1, # 6, p. 819 - 824

  摘要：

  DOI：

文献信息

• Reactivity of [Pt(P^<i>t</i>Bu₃)₂] with Zinc(I/II) Compounds: Bimetallic Adducts, Zn–Zn Bond Cleavage, and Cooperative Reactivity
  作者：Nereida Hidalgo、Carlos Romero-Pérez、Celia Maya、Israel Fernández、Jesús Campos

  DOI：10.1021/acs.organomet.1c00088

  日期：2021.4.26

  use of sterically hindered [Pt(PtBu3)2] (1) to access Pt/Zn bimetallic complexes. Compounds [(PtBu3)2Pt → Zn(C6F5)2] (2) and [Pt(ZnCp*)6] (3) (Cp* = pentamethylcyclopentadienyl) were isolated by reactions with Zn(C6F5)2 and [Zn2Cp*2], respectively. We also disclose the cooperative reactivity of 1/ZnX2 pairs (X = Cl, Br, I, and OTf) toward water and dihydrogen, which can be understood in terms of bimetallic

  基于锌亲电子试剂的纯金属路易斯对 (MOLP) 由于与根岸交叉偶联反应相关而特别令人感兴趣。双金属配合物中的锌基配体还对其所结合的过渡金属具有独特的反应性。在这里，我们探索使用空间位阻 [Pt(P t Bu 3 ) 2 ] ( 1 ) 来获得 Pt/Zn 双金属配合物。通过与 Zn(C 6反应) 分离出化合物 [(P t Bu 3 ) 2 Pt → Zn(C 6 F 5 ) 2 ] ( 2 ) 和 [Pt(ZnCp*) 6 ] ( 3 ) (Cp* = 五甲基环戊二烯基)分别为F 5 ) 2和[Zn 2 Cp* 2 ]。我们还公开了1 /ZnX 2对（X = Cl、Br、I 和 OTf）对水和氢气的协同反应性，这可以用双金属挫败来理解。
• Evidence for Genuine Bimetallic Frustrated Lewis Pair Activation of Dihydrogen with Gold(I)/Platinum(0) Systems
  作者：Nereida Hidalgo、Juan José Moreno、Marina Pérez‐Jiménez、Celia Maya、Joaquín López‐Serrano、Jesús Campos

  DOI：10.1002/chem.201905793

  日期：2020.5.12

  mechanism of dihydrogen activation by a gold(I)/platinum(0) metal-only frustrated Lewis pair (FLP) is described herein. The drastic effects on H2 activation derived from subtle ligand modifications have also been investigated. The importance of the balance between bimetallic adduct formation and complete frustration has been interrogated, providing for the first time evidence for genuine metal-only

  本文描述了联合实验/计算努力，以阐明仅由金（I）/铂（0）金属失意的路易斯对（FLP）激活二氢的机理。还研究了源自微妙的配体修饰对H2活化的剧烈影响。人们一直在质疑双金属加合物形成与完全失意之间平衡的重要性，这首次为溶液中纯金属的纯FLP反应性提供了证据。还已经阐明了强烈的逆动力学同位素效应的起源，为拟议的双金属双金属FLP型裂解提供了进一步的支持。
• Chemistry of phosphine–borane adducts at platinum centers: dehydrocoupling reactivity of Pt(<scp>ii</scp>) dihydrides with P–H bonds
  作者：Cory A. Jaska、Alan J. Lough、Ian Manners

  DOI：10.1039/b416114a

  日期：——

  The reaction of the Pt(II) dihydride complex cis-[PtH2(dcype)] (dcype = 1,2-bis(dicyclohexylphosphino)ethane) with the primary or secondary phosphine–borane adducts PhRPH·BH3 (R = H, Ph) was found to exclusively afford the mono-substituted complexes cis-[PtH(PPhR·BH3)(dcype)] (1: R = H; 2: R = Ph) via a dehydrocoupling reaction between Pt–H and P–H bonds. Similar reactivity was observed between the uncoordinated phosphines PhRPH (R = H, Ph) and cis-[PtH2(dcype)], which gave cis-[PtH(PPhR)(dcype)] (4: R = H; 5: R = Ph). The complexes were characterized by 1H, 11B, 13C and 31P NMR spectroscopy, IR, MS and, in the case of 2, X-ray crystallography that confirmed the cis geometries. The di-substituted complex cis-[Pt(PhPH·BH3)2(dcype)] (3) was prepared from the reaction of cis-[PtCl2(dcype)] with two equivalents of Li[PPhH·BH3]. This suggested that steric reasons alone cannot be used to explain the lack of reactivity with respect to a second dehydrocoupling reaction involving the remaining Pt–H bond in complexes 1, 2, 4 and 5.

  研究发现，铂(II)二酐配合物 cis-[PtH2(dcype)] (dcype = 1,2-双(二环己基膦)乙烷)与一级或二级膦硼烷加合物 PhRPHÂ-BH3 (R = H, Ph)反应，只能生成单取代配合物 cis-[PtH(PPhRÂ- )(dcype)] (1. R = H; 2: R = Ph)：R=H；2：R=Ph）。非配位膦 PhRPH（R = H、Ph）和顺式[PtH2(dcype)]之间也发生了类似的反应，得到了顺式[PtH(PPhR)(dcype)]（4：R = H；5：R = Ph）。这些复合物的特征通过 1H、11B、13C 和 31P NMR 光谱、红外光谱、质谱以及 X 射线晶体学进行了表征。顺式-[Pt(PhpHÂ- )2(dcype)]（3）是由顺式-[PtCl2(dcype)]与两当量 Li[PPhHÂ- ] 反应制备而成的二取代复合物。这表明，在涉及复合物 1、2、4 和 5 中剩余的 PtâH 键的第二次脱氢偶联反应中，不能仅仅用立体原因来解释反应活性的缺乏。
• Isolation of di-μ-iodo-bis(Tri-t-butyl phosphine)-bis(carbonyl) diplatinum: A new dinuclear platinum(I) complex
  作者：Anil B. Goel、Sarla Goel

  DOI：10.1016/0020-1650(80)80042-0

  日期：——
• A Molecular Rotor Possessing an H–M–H “Spoke” on a P–M–P “Axle”: A Platinum(II) <i>trans</i>-Dihydride Spins Rapidly Even at 75 K
  作者：Ernest Prack、Christopher A. O’Keefe、Jeremy K. Moore、Angel Lai、Alan J. Lough、Peter M. Macdonald、Mark S. Conradi、Robert W. Schurko、Ulrich Fekl

  DOI：10.1021/jacs.5b08213

  日期：2015.10.28

  A new class of low-barrier molecular rotors, metal trans-dihydrides, is suggested here. To test whether rapid rotation can be achieved, the known complex trans-H2Pt((PBu3)-Bu-t)(2) was experimentally studied by H-2 and Pt-195 solid-state NMR spectroscopy (powder pattern changes with temperature) and computationally modeled as a (Bu3P)-Bu-t-Pt-(PBu3)-Bu-t stator with a spinning H-Pt-H rotator. Whereas the related chloro-hydride complex, trans-H(Cl)-Pt((PBu3)-Bu-t)(2), does not show rotational behavior at room temperature, the dihydride trans-H2Pt((PBu3)-Bu-t)(2) rotates fast on the NMR time scale, even at low temperatures down to at least 75 K. The highest barrier to rotation is estimated to be similar to 3 kcal mol(-1), for the roughly 3 angstrom long rotator in trans-H2Pt((PBu3)-Bu-t)(2).