bis(diphenylacetylene)platinum(0) | 61771-08-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: bis(diphenylacetylene)platinum(0)
• 英文别名: Pt(diphenylacetylene)₂；Pt(η(2)-diphenylacetylene)；[Pt(diphenylacetylene)2]；[Pt(η2-PhCCPh)2]；2-Phenylethynylbenzene;platinum
• CAS: 61771-08-2
• 化学式: C₂₈H₂₀Pt
• 分子量: 551.547
• InChiKey: LPJDJRBJIOFUOK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.17
• 重原子数：
  29
• 可旋转键数：
  4
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  乙烯双(三苯基磷)铂 、 bis(diphenylacetylene)platinum(0) 以 light petroleum 为溶剂， 以18%的产率得到[Pt3(μ-PhC2Ph)2(PPh3)4]
  参考文献：
  名称：

  铂的炔烃配合物。第4部分。逐步形成具有桥联炔配体的二铂和三铂配合物；的[铂晶体结构3 {μ-（η 2 -PhC 2 PH）} 2（PET 3）4 ]

  摘要：

  化合物[Pt（PhC 2 Ph）2 ]与[Pt（C 2 H 4）（PPh 3）2 ]或[Pt 2（µ-cod）（PEt 3）4 ]的反应（cod =环八- 1,5-二烯）提供二铂配合物[Pt 2（µ-PhC 2 Ph）（PhC 2 Ph）（PR 3）2 ]（R = Ph或Et）。三苯基膦化合物也已经通过用[Pt（C 2 H 4）2（PPh 3）]处理PhC CPh而制备。[Pt 2（µ-PhC 2Ph）（PhC 2 Ph）（PPh 3）2 ]与[Pt（C 2 H 4）（PPh 3）2 ]处理时结合第三个铂原子，得到三铂络合物[Pt 3（µ-PhC 2 Ph）2（PPh 3）4 ]。后者也可以通过将2摩尔当量的[Pt（C 2 H 4）（PPh 3）2加到[Pt（PhC 2 Ph）2 ]中来制备，同样使用[Pt 2（µ-cod）（PEt 3）4 ]。鉴于这些化合物的新颖性，已经对[Pt 3（µ-PhC

  DOI：

  10.1039/dt9800002182
• 作为产物：
  描述：

  {Pt(PhCCPh)(PEt3)2} 、 二苯基乙炔 在 氧气 作用下， 以 甲苯 为溶剂， 以67%的产率得到bis(diphenylacetylene)platinum(0)
  参考文献：
  名称：

  Palladacycle Chemistry on the Edge of Naphthalene and Triphenylene:  Alkyne Cycloadditions and Autocatalytic Coupling

  摘要：

  The four-membered palladacycle Pd(PEt3)(2)(1,8-naphthalenediyl) (3) and the five-membered palladacycle Pd(PEt3)(2)(1,12-triphenylenediyl) (4) were prepared from Pd(PEt3)(2)Cl-2 and the appropriate dilithio reagent. Both palladacycles are thermally unstable, decomposing autocatalytically at 100 degrees C to palladium black, Pd(PEt3)(3), and perylene (for 3) or dinaphtho[def,pqr]tetraphenylene (for 4). In the presence of PhCCPh, the decomposition is slowed and the cycloaddition products 1,2-diphenylacenapthylene (for 3) and 4,5-diphenylbenzo[e]pyrene (for 4) are formed, along with the decomposition products. Kinetic data again indicate autocatalytic behavior. The decomposition and cycloaddition reactions are faster in the presence of dioxygen but are arrested by the addition of PEt3 or mercury, consistent with colloidal palladium (detected by TEM) catalysis. Further reactions of the previously reported platinum analogue of 3 are also reported. The thermally stable platinacycle Pt(PEt3)(2)(1,8-naphthalenediyl) (1) decomposes at 120 degrees C in the presence of colloidal platinum, yielding perylene, platinum black, and platinum(0) phosphine complexes. Complex 1 also decomposes in wet toluene, and the colloidal platinum catalyzed cycloaddition reaction of 1 with PhCCPh is promoted by water. Interestingly, colloidal platinum also appears to catalyze the decomposition and alkyne cycloaddition reactions of palladacycle 3. Finally, heating alkyne complex Pt(PEt3)(2)(eta(2)-PhCCPh) with O-2 and PhCCPh gives Pt(eta(2)-PhCCPh)(2) in good yield.

  DOI：

  10.1021/om061071v

文献信息

• Synthesis of a Novel Volatile Platinum Complex for Use in CVD and a Study of the Mechanism of Its Thermal Decomposition in Solution
  作者：Christopher D. Tagge、Robert D. Simpson、Robert G. Bergman、Michael J. Hostetler、Gregory S. Girolami、Ralph G. Nuzzo

  DOI：10.1021/ja9526527

  日期：1996.1.1

  reversible β-hydride elimination followed by reversible dissociation of 1,4-pentadiene to give a 3-coordinate platinum hydride intermediate (9). Reductive elimination of 1-pentene from 9 deposits metallic platinum. The rate of decomposition exhibits a significant β-deuterium isotope effect of kH/kD = 3.8 ± 0.3. Added olefins are rapidly isomerized during the decomposition of 1; trap...

  描述了顺式双 (η2,η1-pent-4-en-1-yl) 铂 (1) 在芳香族溶剂中热分解的合成、表征、化学气相沉积和机理研究。配合物 1 具有独特的螯合结构，增加了挥发性，并已证明可用于在温和条件下化学气相沉积铂薄膜。在 175 °C 的热壁玻璃管中，在载玻片上沉积的薄膜的元素组成为 82% Pt 和 18% C。动力学、氘标记和化学捕获实验表明，1 在芳香族溶剂中的分解是可逆的β-氢化物消除，然后 1,4-戊二烯可逆解离，得到 3-配位的氢化铂中间体 (9)。从 9 个沉积金属铂中还原消除 1-戊烯。分解速率表现出明显的 β-氘同位素效应，kH/kD = 3.8 ± 0.3。加入的烯烃在 1 的分解过程中迅速异构化；陷阱...
• Platinum(II) Di-ω-alkenyl Complexes as “Slow-Release” Precatalysts for Heat-Triggered Olefin Hydrosilylation
  作者：Sumeng Liu、Gregory S. Girolami

  DOI：10.1021/jacs.1c06846

  日期：2021.10.27

  high anti-Markovnikov selectivity are a result of the slow release of 1 from 1-COD at room temperature, so that the concentration of Pt0 during the initial stages of the catalysis is negligible. As a result, formation of colloidal Pt, which is known to cause side reactions, is minimized, and the amounts of side products are very small and comparable to those seen for platinum(0) carbene catalysts. The

  我们描述了化学计量 PtR 2的铂 (II) 二-ω-烯基化合物的合成、表征和催化氢化硅烷化活性，其中 R = CH 2 SiMe 2 (乙烯基) ( 1 ) 或 CH 2 SiMe 2 (烯丙基) ( 2 )，以及它们与 1,5-环辛二烯 (COD)、二苯并 [ a , e ] 环辛四烯 (DBCOT) 和降冰片二烯 (NBD) 的加合物，它们可被视为反应性化合物1和2的缓释来源。负载量为 0.5 × 10 –6 –5 × 10 –6 mol %，1-COD是一种具有热触发潜伏期的活性氢化硅烷化催化剂：即使在 20 °C 下数小时后，对许多烯烃底物也不会发生氢化硅烷化活性，但在 50 °C 下 4 小时后可观察到高达 200000 的转换数，具有出色的选择性反马尔科夫尼科夫积的形成。Pt II预催化剂的活化通过三个步骤进行：COD 从 1-COD 缓慢解离形成 1，1与硅烷快速反应，以及消除两个
• Two Alternative, Convenient Routes to Bis(diphenylacetylene)platinum(0)
  作者：Christian Huber、Akshay Kokil、Walter R. Caseri、Christoph Weder

  DOI：10.1021/om020230h

  日期：2002.9.1

  Two new synthetic routes are presented that allow the convenient preparation and isolation of bis(diphenylacetylene)platinum(0) under ambient conditions. The first procedure is based on a ligand exchange reaction between Ph−C⋮C−Ph and tris(styrene)platinum(0). The second framework relies on the reduction of cis-[PtCl2(PhCHCH2)2] with triphenylsilane in the presence of diphenylacetylene.

  提出了两种新的合成路线，这些路线允许在环境条件下方便地制备和分离双（二苯基乙炔）铂（0）。第一个步骤基于Ph-C⋮C-Ph与三（苯乙烯）铂（0）之间的配体交换反应。第二个框架依赖于在二苯基乙炔存在下用三苯基硅烷还原顺式-[PtCl 2（PhCH CH 2）2 ]。
• Chelating P,N versus P,P Ligands:  Differing Reactivity of Donor-Stabilized Pt(η²-PhC⋮CPh) Complexes Toward Diphenylacetylene
  作者：Christian Müller、Rene J. Lachicotte、William D. Jones

  DOI：10.1021/om010924a

  日期：2002.3.1

  The thermal activation of the eta(2)-diphenylacetylene complex (PN)Pt(eta(2)-PhC=CPh) (1) (PN = (diisopropylphosphinodimethylamino)ethane leads to the formation of the platinacyclopenta-2,4-diene compound (PN)Pt(CPh)(4) (3), which can be quantitatively obtained by reaction of 1 with 1 equiv of diphenylacetylene. Two transient intermediates are observed by P-31 NMR spectroscopy during the course of the latter reaction. These species were independently synthesized and characterized. Hexaphenylbenzene is catalytically generated by reaction of 1 in the presence of excess diphenylacetylene. In contrast, no reaction of diphenylacetylene with (dippe)Pt(eta(2)-PhC=CPh) (2) (dippe = bis(diisopropylphosphino)ethane) was observed.
• Chandra, Grish; Lo, Peter Y.; Hitchcock, Peter B., Organometallics, 1987, vol. 6, # 1, p. 191 - 192
  作者：Chandra, Grish、Lo, Peter Y.、Hitchcock, Peter B.、Lappert, Michael F.

  DOI：——

  日期：——