diphenyl(triphenylstannylmethyl)phosphane | 182366-92-3

• 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: diphenyl(triphenylstannylmethyl)phosphane
• CAS: 182366-92-3
• 化学式: C₃₁H₂₇PSn
• 分子量: 549.239
• InChiKey: XBPQHOXRJZKMTN-UHFFFAOYSA-N

物化性质

• 沸点：
  581.8±52.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.83
• 重原子数：
  33.0
• 可旋转键数：
  7.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.03
• 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：

  diphenyl(triphenylstannylmethyl)phosphane 、 diiron nonacarbonyl 以 甲苯 为溶剂， 以62%的产率得到
  参考文献：
  名称：

  Transition Metal Stannyl Complexes. 11.¹ Chelated ((Phosphinoalkyl)stannyl)iron Complexes by Intramolecular Oxidative Addition of Tin−Phenyl or Tin−Methyl Groups

  摘要：

  Reaction of Fe-2(CO)(9) with Ph(2)P(CH2)(n)SnR(2)R' (n = 2, R' = Ph, SnR(2) = SnPh(2) = SnPhMe, R' = Me, SnR(2) = SnMe(2); n = 1, 3, SnR(2)R' = SnPh(3)) results in the formation of(CO)(5-x)Fe[PPh(2)(CH2)(n)SnR(2)R'](x) (x = 1, 2). Upon UV irradiation, the chelated (phosphinoalkyl)-stannyl complexes (CO)(3)(R')FePPh(2)(CH2)(n)SnR(2) are obtained by intramolecular oxidative addition of the Sn-R' group. The complexes mer-(CO)(3)(H)(R'Si-3)FePPh(2)(CH2)(3)SnPh(3) (SiR'(3) = SiMePh(2), Si(OMe)(3)) are formed at -50 degrees C from (CO)(4)Fe(H)SiR'(3) and Ph(2)P(CH2)(2)SnPh(3). While the SiMePh(2) derivative is converted to the chelated complex (CO)(3)(Ph)FePPh(2)-(CH2)(2)SnPh(2) by HSiMePh(2) elimination upon heating, the Si(OMe)(3) derivative does not give the intramolecular oxidative addition. Photochemical reaction of (CO)(3)(Ph)FePPh(2)-(CH2)(2)SnPh(2) with Ph(2)P(CH2)(2)SnPh(3) gives the substitution product (CO)(2)(Ph)Fe[PPh(2)-(CH2)(2)SnPh(2)]PPh(2)(CH2)(2)SnPh(3). While a second oxidative addition to the iron center by the dangling SnPh(3) group is not possible, the Sn-Ph group readily adds to a (Ph(3)P)(2)Pt fragment to give (CO)(2)(Ph)Fe[PPh(2)(CH2)(2)SnPh(2)]PPh(2)(CH2)(2)SnPh(2)Pt(Ph)(PPh(3))(2). The related complex (CO)(3)(H)[(MeO)(3)Si]FePPh(2)(CH2)(2)SnPh(2)Pt(Ph)(PPh(3))(2) is similarly obtained from (CO)(3)(H)[(MeO)(3)-Si]FePPh(2)(CH2)(2)SnPh(3).

  DOI：

  10.1021/om960424v
• 作为产物：
  描述：

  (lithiomethyl)diphenylphosphane 、 三苯基氯化锡 以 四氢呋喃 为溶剂， 以62%的产率得到diphenyl(triphenylstannylmethyl)phosphane
  参考文献：
  名称：

  Transition Metal Stannyl Complexes. 11.¹ Chelated ((Phosphinoalkyl)stannyl)iron Complexes by Intramolecular Oxidative Addition of Tin−Phenyl or Tin−Methyl Groups

  摘要：

  Reaction of Fe-2(CO)(9) with Ph(2)P(CH2)(n)SnR(2)R' (n = 2, R' = Ph, SnR(2) = SnPh(2) = SnPhMe, R' = Me, SnR(2) = SnMe(2); n = 1, 3, SnR(2)R' = SnPh(3)) results in the formation of(CO)(5-x)Fe[PPh(2)(CH2)(n)SnR(2)R'](x) (x = 1, 2). Upon UV irradiation, the chelated (phosphinoalkyl)-stannyl complexes (CO)(3)(R')FePPh(2)(CH2)(n)SnR(2) are obtained by intramolecular oxidative addition of the Sn-R' group. The complexes mer-(CO)(3)(H)(R'Si-3)FePPh(2)(CH2)(3)SnPh(3) (SiR'(3) = SiMePh(2), Si(OMe)(3)) are formed at -50 degrees C from (CO)(4)Fe(H)SiR'(3) and Ph(2)P(CH2)(2)SnPh(3). While the SiMePh(2) derivative is converted to the chelated complex (CO)(3)(Ph)FePPh(2)-(CH2)(2)SnPh(2) by HSiMePh(2) elimination upon heating, the Si(OMe)(3) derivative does not give the intramolecular oxidative addition. Photochemical reaction of (CO)(3)(Ph)FePPh(2)-(CH2)(2)SnPh(2) with Ph(2)P(CH2)(2)SnPh(3) gives the substitution product (CO)(2)(Ph)Fe[PPh(2)-(CH2)(2)SnPh(2)]PPh(2)(CH2)(2)SnPh(3). While a second oxidative addition to the iron center by the dangling SnPh(3) group is not possible, the Sn-Ph group readily adds to a (Ph(3)P)(2)Pt fragment to give (CO)(2)(Ph)Fe[PPh(2)(CH2)(2)SnPh(2)]PPh(2)(CH2)(2)SnPh(2)Pt(Ph)(PPh(3))(2). The related complex (CO)(3)(H)[(MeO)(3)Si]FePPh(2)(CH2)(2)SnPh(2)Pt(Ph)(PPh(3))(2) is similarly obtained from (CO)(3)(H)[(MeO)(3)-Si]FePPh(2)(CH2)(2)SnPh(3).

  DOI：

  10.1021/om960424v

文献信息

• “A posteriori” modification of carbosilane dendrimers and dendrons: their activation in core and branch positions
  作者：Arno Tuchbreiter、Helmut Werner、Lutz H. Gade

  DOI：10.1039/b501069a

  日期：——

  The introduction of phenyl groups at different points on carbosilane dendrimers allows their acidolytic conversion to highly reactive triflato groups which in turn are readily substituted by anionic nucleophiles. Core phenylated first–fourth generation dendrimers were synthesized from tri(allyl)phenylsilane by an alternating sequence of hydrosilylation and allylation steps. Similarly, carbosilane dendrimers containing phenyl-Si groups at the branching points and in the periphery were prepared from tetraallylsilane which was hydrosilylated with PhHSiCl2. Reaction of the phenylated dendrimers with triflic acid in toluene cleanly gave the silyl triflate derivatives, provided that the correct stoichiometry of the reagents was used. In the presence of a large excess of triflic acid the SiMe3-end groups are slowly converted to SiMe2(OTf)-units. The proof of concept was provided by the fixation of a Ph2PCH2} group using the lithiated diphenylphosphinomethanide Ph2PCH2Li, obtained by cleavage of Ph3SnCH2PPh2 with PhLi, as well as a lithiated ether-alcohol functionalized triphos derivative to the core of a third generation carbosilane dendrimer.

  在碳硅烷树枝状聚合物上的不同点引入苯基使得它们能够酸解转化为高反应性的三氟甲磺酸根基团，而三氟甲磺酸根基团又很容易被阴离子亲核试剂取代。通过交替顺序的氢化硅烷化和烯丙基化步骤，由三(烯丙基)苯基硅烷合成了核心苯基化的第一至第四代树枝状聚合物。类似地，由用PhHSiCl 2 氢化硅烷化的四烯丙基硅烷制备在支化点和外围含有苯基-Si基团的碳硅烷树枝状聚合物。只要使用正确的试剂化学计量，苯代树枝状聚合物与三氟甲磺酸在甲苯中的反应干净地得到三氟甲磺酸甲硅烷基酯衍生物。在大量过量的三氟甲磺酸存在下，SiMe3-端基缓慢转化为SiMe2(OTf)-单元。通过使用锂化二苯基膦甲烷化物 Ph2PCH2Li（通过用 PhLi 裂解 Ph3SnCH2PPh2 获得）将 Ph2PCH2} 基团以及锂化醚醇官能化三磷衍生物固定到第三代碳硅烷树枝状聚合物的核心，提供了概念验证。