[(PPh3)2Pt(η3-CH2CHCH2)]OSO2CF3 | 790225-26-2

• 英文名称: [(PPh3)2Pt(η3-CH2CHCH2)]OSO2CF3
• CAS: 790225-26-2
• 化学式: CF₃O₃S*C₃₉H₃₅P₂Pt
• 分子量: 909.805
• InChiKey: KBMJISLOQFNBGQ-UHFFFAOYSA-M

反应信息

• 作为产物：
  描述：

  [(PPh3)2Pt(η3-CH2C(OCHCHMe)CHPh)]OSO2CF3 以 苯 为溶剂， 生成 [(PPh3)2Pt(η3-CH2CHCH2)]OSO2CF3
  参考文献：
  名称：

  Reactions of [(PPh3)2Pt(η3-CH2CCPh)]+ with oxygen nucleophiles and chemistry of resultant [(PPh3)2Pt(η3-CH2C(OR)CHPh)]+ complexes

  摘要：

  The eta(3)-allenyl/propargyl complex [(PPh3)(2)Pt(eta(3)-CH2CCPh)]OTf (1OTf) undergoes addition reactions with a number of oxygen nucleophiles in CH2Cl2 solution at ambient temperature. With H2O, it yields the binuclear oxygen-bridged eta(3)-allyl [{(PPh3)(2)Pt(eta(3)-CH2CCHPh)}(2)O](OTf)(2) (2(OTf)(2)). With primary and secondary alcohols, it rapidly affords the eta(3)-(2-alkoxyallyl) complexes [(PPh3)(2)Pt(eta(3) -CH2C(OR)CHPh)]OTf (R = Et (3OTf), i-Pr (4OTf), CH2CMe3 (5OTf), CH2CH=CH2 (7OTf)), whereas with tertiary alcohols, in slower reactions, it gives both 2(OTf)(2) and [(PPh3)(2)Pt(eta(3)-CH2C(OR)CHPh)]OTf (R = CMe3, C(Me)(2)Et (6OTf)). There is no reaction at ambient temperature between 1OTf and phenols; however, 1OTf and PhOH afford [(PPh3)(2)Pt(eta(3)-CH2C(OPh)CHPh)]OTf (8OTf) in the presence of NEt3. Competition studies reveal the following reactivity order, attributed to steric effects: Me3CCH2OH(1.0) < i-PrOH(1.2) < EtOH(2.1) < MeOH(4.3). The eta(3)-(2-alkoxyallyl) complexes react with NaOMe to yield the eta(3)-oxatrimethylemethane product (PPh3)(2)Pt(eta(3)-CH2C(O)CHPh) (10), which was also obtained by reaction of 2(OTf)(2) with two equivalents of NaOMe and of 1OTf with NaOH. Complex 10 undergoes conversion to the appropriate [(PPh3)(2)Pt(eta(3)-CH2C(OR)CHPh)](+) with [Et3O]PF6, (MeO)(2)SO2 and MeI. The eta(3)-(2-allyloxyallyl) 7OTf reacts with (PPh3)(2)Pt(C2H4) to give 10 and [(PPh3)(2)Pt(eta(3)-CH2CHCH2)]OTf; thermolysis of 7OTf in toluene at reflux furnishes [(PPh3)(2)Pt(eta(3)-CH2CHCH2)]OTf, whereas heating in benzene-chloroform affords [(PPh3)(2)Pt(eta(3)-CH2C(OCH=CHMe)CHPh)]OTf (11OTf). which results from isomerization of OCH2CH=CH2 to OCH=CHMe. Reaction pathways have been suggested for a number of the aforementioned transformations. All new complexes were characterized by a combination of elemental analysis, FAB mass spectrometry and H-1-, C-13{H-1}- and P-31{H-1}-NMR spectroscopy. They were assigned structures in which the eta(3)-allyl oxygen and Ph groups are syn from the H-1-NMR spectra. (C) 2002 Elsevier Science B.V. All rights reserved.

  DOI：

  10.1016/s0022-328x(02)01556-5