trans-(p-tolyl)(P(p-tolyl)3)2Pt(triethylsilylhexatriynyl) | 244075-60-3

• 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: trans-(p-tolyl)(P(p-tolyl)3)2Pt(triethylsilylhexatriynyl)
• 英文别名: trans-(p-tol)(p-tol3P)2 platinum(II) (CC)3Si(Et3)；Methylbenzene;platinum(2+);triethyl(hexa-1,3,5-triynyl)silane;tris(4-methylphenyl)phosphane
• CAS: 244075-60-3
• 化学式: C₆₁H₆₄P₂PtSi
• 分子量: 1082.29
• InChiKey: DLSCXQNNNSNMEH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  13.16
• 重原子数：
  65
• 可旋转键数：
  12
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.21
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  trans-(p-tolyl)(P(p-tolyl)3)2Pt(triethylsilylhexatriynyl) 在 四丁基氟化铵 作用下， 以 四氢呋喃 为溶剂， 以84%的产率得到trans-(p-tol)(p-tol3P)2 platinum(II) (CC)3H
  参考文献：
  名称：

  C₈ and C₁₂ sp Carbon Chains That Span Two Platinum Atoms:  The First Structurally Characterized 1,3,5,7,9,11-Hexayne

  摘要：

  Reaction sequences involving trans-(p-tol)-(Ar3P)(2)PtCl (Ar = Ph, p-tol), HC=CC=CH, HC=CSiEt3, and oxidative =CH/HC= cross- or homocoupling (O-2, cat. CuCl/TMEDA) give the C-x complexes trans,trans-(p-tol)(Ar3P)(2)Pt(C=C)(n)Pt(PAr3)(2)(p-tol) (n = 4, 6), which have been characterized by crystallography and by IR, NMR, and UV-visible spectroscopy.

  DOI：

  10.1021/om990448c
• 作为产物：
  描述：

  三乙基矽乙炔 、 trans-(p-tol)(p-tol3P)2 platinum(II) (CC)2H 在 四甲基乙二胺 、 氧气 、 copper(l) chloride 作用下， 以 丙酮 为溶剂， 以83%的产率得到trans-(p-tolyl)(P(p-tolyl)3)2Pt(triethylsilylhexatriynyl)
  参考文献：
  名称：

  C₈ and C₁₂ sp Carbon Chains That Span Two Platinum Atoms:  The First Structurally Characterized 1,3,5,7,9,11-Hexayne

  摘要：

  Reaction sequences involving trans-(p-tol)-(Ar3P)(2)PtCl (Ar = Ph, p-tol), HC=CC=CH, HC=CSiEt3, and oxidative =CH/HC= cross- or homocoupling (O-2, cat. CuCl/TMEDA) give the C-x complexes trans,trans-(p-tol)(Ar3P)(2)Pt(C=C)(n)Pt(PAr3)(2)(p-tol) (n = 4, 6), which have been characterized by crystallography and by IR, NMR, and UV-visible spectroscopy.

  DOI：

  10.1021/om990448c

文献信息

• Syntheses, Structures, and Electronic and Photophysical Properties of Unsymmetrically Substituted Butadiynediyl and Hexatriynediyl Complexes Derived from (C₆F₅)(R₃P)₂Pt, (<i>p</i>-tol)(R₃P)₂Pt, and (Ph₃P)Au End-Groups
  作者：Laura de Quadras、Abigail H. Shelton、Helene Kuhn、Frank Hampel、Kirk S. Schanze、John A. Gladysz

  DOI：10.1021/om800493x

  日期：2008.10.13

  butadiynyl complex trans-(C6F5)(Et3P)2Pt(C≡C)2H (6) and trans-(p-tol)(Et3P)2PtCl (7) in HNEt2 affords trans,trans-(C6F5)(Et3P)2Pt(C≡C)2Pt(PEt3)2(p-tol) (8; 62%), but similar reactions of p-tol3P-substituted coupling partners, or of 6 and trans-(p-tol)(p-tol3P)2PtCl (4), are not successful. However, 6 and 4 react under modified conditions (t-BuOK, KPF6, cat. CuCl, THF/methanol) to give trans,trans-(C6F5)(Et3

  CuCl催化的丁二炔基复合物反式-（C 6 F 5）（Et 3 P）2 Pt（C≡C）2 H（6）和反式-（对甲苯基）（Et 3 P）2 PtCl（7）的反应）在HNEt 2中提供反式，反式-（C 6 F 5）（Et 3 P）2 Pt（C≡C）2 Pt（PEt 3）2（对甲苯基）（8 ; 62％），但与p -tol 3 P取代的偶合伴侣或6和反式-（p -tol）（p -tol 3 P）2 PtCl（4）均不成功。但是，6和4在修饰的条件下（t -BuOK，KPF 6，催化剂CuCl，THF /甲醇）反应生成反式，反式-（C 6 F 5）（Et 3 P）2 Pt（C≡C）2铂（P p -tol 3）2（p-tol）（9 ; 91％）。所述hexatriynyl络合物的反式- （C 6 ˚F 5）（R 3 P）2的Pt（C≡C）3 H（R = p -tol，等）与处理过的4和7，分别是原始或
• A Synthetic Breakthrough into an Unanticipated Stability Regime:  Readily Isolable Complexes in which C₁₆−C₂₈ Polyynediyl Chains Span Two Platinum Atoms
  作者：Qinglin Zheng、J. A. Gladysz

  DOI：10.1021/ja0534598

  日期：2005.8.1

  The oxidative cross-coupling of trans-(p-tol)(p-tol3P)2Pt(CC)2H (PtC4H) and excess H(CC)2SiEt3 (O2, cat. CuCl, TMEDA, acetone; Hay conditions) gives PtC8Si (29%), PtC12Si (30%), and PtC16Si (1%; Si = SiEt3). The less stable PtC6H is generated in situ from PtC6Si and n-Bu4N+F-; following the addition of ClSiMe3 (F- scavenger) and excess H(CC)2SiEt3, the Hay conditions afford PtC10Si (59%) and PtC14Si (7%). Analogous sequences can be conducted with PtC8Si and PtC10Si. When PtC6Si, PtC8Si, and PtC10Si are similarly reacted in the absence of H(CC)2SiEt3, homocouplings to PtC12Pt (88%), PtC16Pt (70%), and PtC20Pt (72%) occur. However, analogous reactions of PtC12Si and PtC14Si fail, presumably due to the rapid decomposition of PtC12H and PtC14H. Brønsted acidity trends suggest that (CC)n moieties should become better leaving groups with increasing chain length. Thus, when PtC12Si and PtC14Si are subjected to the Hay conditions alone, PtC24Pt (36%) and PtC28Pt (51%) are isolated, with substantial recovery of starting material from the former reaction. Presumably adventitious water and/or other nucleophiles effect desilylation (as also seen in the cross-couplings), after which homocoupling is rapid due to the simultaneous availability of an oxidizing agent. PtC24Pt and PtC28Pt are thermally stable to >/=140 degrees C, whereas all other known dodecaynes and tetradecaynes rapidly decompose at room temperature. There is every reason to believe that this series can be further extended. UV-visible spectra show progressively red-shifted and more intense bands with epsilon > 400 000 M-1 cm-1.