{Pt(PhCCPh)(PEt3)2} | 75983-00-5

• 英文名称: {Pt(PhCCPh)(PEt3)2}
• 英文别名: (diphenylacetylene)bis(triethylphosphine)platinum(0)；[Pt(η2-PhCCPh)(PEt3)2]；Pt(PEt3)2(η2-PhCCPh)
• CAS: 75983-00-5
• 化学式: C₂₆H₄₀P₂Pt
• 分子量: 609.631
• InChiKey: AYEYQUOHKMZLAL-UHFFFAOYSA-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(PhCCPh)(PEt3)2} 、 溶剂黄146 以 溶剂黄146 为溶剂， 以80%的产率得到2-phenylethenylbenzene;platinum(2+);triethylphosphane;acetate
  参考文献：
  名称：

  用羧酸和第 10 族过渡金属配合物对炔烃进行简便的区域和立体选择性加氢金属化：用甲酸对炔烃进行选择性加氢

  摘要：

  通过炔烃、羧酸和零价族 10 过渡金属络合物 M(PEt(3))(4) (M =镍、钯、铂）。一项机理研究表明，氢金属化不是通过炔烃与由羧酸与 Pt(PEt(3))(4) 质子化产生的氢化金属反应进行的，而是通过炔烃配位金属络合物与酸。这一发现阐明了长期以来提出的反应机制，该机制通过生成烯基钯中间体和随后在由 Brφnsted 酸和 Pd(0) 配合物的组合催化的各种反应中转化该配合物来进行。

  DOI：

  10.1021/ja2069246
• 作为产物：
  描述：

  trans-hydrido(nitrato)bis(triethylphosphine)platinum(II) 以 四氢呋喃 、 氘代苯 、 苯 为溶剂， 生成 {Pt(PhCCPh)(PEt3)2}
  参考文献：
  名称：

  Syntheses, reactions, and molecular structures of trans-hydrido(phenylamido)bis(triethylphosphine)platinum(II) and trans-hydridophenoxobis(triethylphosphine)platinum(II)

  摘要：

  DOI：

  10.1021/ja00195a031

文献信息

• Syntheses, Structures, and Reductive Elimination Studies of Six-Membered Diaryl Platinacycle Complexes
  作者：Robert Robinson、Paul R. Sharp

  DOI：10.1021/om901033z

  日期：2010.3.22

  (dppp), 4,4′-bis-tert-butyl-2,2′-bipyridine (tBu2bpy)), have been prepared from cis-PtL2Cl2 and the appropriate dilithio reagents. Reductive elimination studies on the platinacycles with L = PEt3 show that the bridging group (X) dramatically influences the reductive elimination rate. Thermodynamic activation parameters were determined for the platinacycles and showed a ΔH⧧ trend X = NMe ≪ O < CH2 with an

  六元铂盐环化合物PtL 2（C 6 H 4 XC 6 H 4）（X = CH 2，O，NMe; L = PEt 3，L 2 = 1,3-双（二苯基膦基）丙烷（dppp），4，由顺式-PtL 2 Cl 2和适当的二硫代试剂制备了4'-双-叔丁基-2,2'-联吡啶（t Bu 2 bpy）。L = PEt 3的platinacycles的还原消除研究表明桥接基团（X）极大地影响了还原消除率。热力学激活参数被确定为platinacycles并呈现出Δ ħ ⧧趋势X = NME«0
• Highly Selective Markovnikov Addition of Hypervalent<i>H</i>-Spirophosphoranes to Alkynes Mediated by Palladium Acetate: Generality and Mechanism
  作者：Li-Biao Han、Yutaka Ono、Qing Xu、Shigeru Shimada

  DOI：10.1246/bcsj.20100141

  日期：2010.9.15

  Palladium acetate efficiently catalyzes the addition of an H-spirophosphorane (pinacolato)2PH to alkynes to give Markovnikov addition products highly selectively. The addition products can be easily converted to the corresponding alkenylphosphonates and phosphonic acids via simple hydrolysis or thermal decomposition. This new reaction is a general method for the introduction of phosphorus functionality to the internal carbons of terminal alkynes, resolving the problem of the regioselectivity associated with hydrophosphorylation reactions so far reported. Mechanistic studies confirmed that (a) palladium acetate was reduced to metallic palladium by H-spirophosphorane, (b) the P–H bond of H-spirophosphorane could be activated by zero-valent platinum complexes to give the corresponding hydridoplatinum complexes, and (c) an alkenylpalladium species was identified from the reaction of palladium acetate with H-spirophosphorane and diphenylacetylene. These results support a reaction mechanism that palladium acetate was first reduced by H-spirophosphorane to give zero-valent palladium. This zero-valent palladium might insert into the P–H bond of the H-spirophosphorane to give a hydridopalladium species which then added to alkyne via the addition of H–Pd bond to form an alkenylpalladium species with the hydrogen atom added to the terminal carbon of alkynes. Reductive elimination of the alkenylpalladium affords the addition product.

  乙酸钯能高效催化H-螺磷烷（pinacolato）2PH与炔烃反应,高选择性地得到马氏加成产物。该加成产物通过简单的水解或热分解即可转化为相应的烯基膦酸盐和膦酸。这一新反应为解决端炔的内碳原子亲核膦化反应的区域选择性问题提供了一般性的方法。机理研究表明：（a）乙酸钯被H-螺磷烷还原为金属钯;（b）零价铂配合物可活化H-螺磷烷的P-H键,生成相应的氢铂配合物;（c）乙酸钯与H-螺磷烷和二苯基乙炔反应生成了烯基钯物种。这些结果支持下列反应机理：乙酸钯首先被H-螺磷烷还原为零价钯,后者插入H-螺磷烷的P-H键生成氢钯物种,该氢钯物种与炔烃反应时, H-Pd键加成形成烯基钯物种,其中的氢原子加成到炔烃的末端碳原子上,最后经还原消除生成加成产物。
• Electrochemical generation and reactivity of bis(tertiary phosphine)platinum(0) complexes: a comparison of the reactivity of [Pt(PPh3)2] and [Pt(PEt3)2] equivalents
  作者：Julian A. Davies、Cassandra T. Eagle、Deborah E. Otis、Uma Venkataraman

  DOI：10.1021/om00106a032

  日期：1989.4
• Autocatalytic Alkyne Cycloadditions:  Evidence for Colloidal Pt Catalysis
  作者：Rowshan Ara Begum、Nripen Chanda、T. V. V. Ramakrishna、Paul R. Sharp

  DOI：10.1021/ja054863+

  日期：2005.10.1

  Treatment of the four-membered platinacycle L2Pt(1,8-naphthalendiyl) (1) or the five-membered platinacycle L2Pt(1,12-triphenylendiyl) with excess PhCCPh at 120-150 degrees C gives the coupling products 1,2-diphenylacenaphthalene or 4,5-diphenylbenzo[e]pyrene and the alkyne complex L2Pt(eta2-PhCCPh). Both reactions show an accelerating rate, which has been traced to catalysis of the reaction by colloidal platinum formed by the reaction of O2 with L2Pt(eta2-PhCCPh).
• Boag, Neil M.; Green, Michael; Grove, David M., Journal of the Chemical Society, Dalton Transactions
  作者：Boag, Neil M.、Green, Michael、Grove, David M.、Howard, Judith A. K.、Spencer, L.、Stone, Gordon A.

  DOI：——

  日期：——