[Rh(triphos)(η(4)-2-S(C6H4)CHCH2CPh3)](PF6) | 164165-88-2

• 英文名称: [Rh(triphos)(η(4)-2-S(C6H4)CHCH2CPh3)](PF6)
• CAS: 164165-88-2
• 化学式: C₆₈H₆₁P₃RhS*F₆P
• 分子量: 1251.09
• InChiKey: VSXAJHTYBMHXEB-HWIPGRMWSA-N

反应信息

• 作为反应物：
  描述：

  [Rh(triphos)(η(4)-2-S(C6H4)CHCH2CPh3)](PF6) 在 cobaltocene 作用下， 以 二氯甲烷 为溶剂， 生成 (triphos)Rh(η(3)-2-vinylthiophenolate)
  参考文献：
  名称：

  含CS键的苯并[b]噻吩在铑和铱配合物中的氧化还原诱导的转化途径

  摘要：

  The thermally generated 16-electron fragments [(triphos)MH] (M = Rh, Ir) react with benzo[b]thiophene by C-S bond scission to yield the 2-vinylthiophenolate derivatives (triphos)M[eta(3)-S(C6H4)CH=CH2] (M = Rh, 1; Ir, 2) which display a rich redox-induced reactivity [triphos = MeC(CH(2)PPh(2))(3)]. Removal of one electron from 1 or 2 leads to the corresponding paramagnetic cations 1(+) and 2(+), respectively; these compounds undergo a radical reaction with H in solution to form the diamagnetic 2-ethylidenecyclohexadienethione complexes anti-[(triphos)M{eta(4)-S(C6H4)CH(CH3)}](+) (M = Rh, anti-3(+); Ir, anti-6(+)) which isomerize to syn-3(+) and syn-6(+), respectively. Addition of one electron to syn-3(+) and syn-6(+) gives the neutral paramagnetic derivatives syn-[(triphos)M{eta(4)-S(C6H4)CH(CH3)}] (M = Rh, syn-3; Ir, syn-6) which convert back to the starting complexes 1 and 2 by homolytic C-H bond cleavage liberating H., and thus completing a full electrochemical cycle by addition elimination of one electron and one H atom. The related 2-(3,3,3-triphenylpropylidene)cyclohexadienethione complex [(triphos)Rh{eta(4)-S(C6H4)CH(CH(2)CPh(3))}]PF6 (4PF(6)) undergoes similar reactions including loss of a trityl radical by a C-C bond cleavage reaction in the neutral derivative (triphos)Rh{eta(4)-S(C6H4)CH(CH(2)CPh(3))} (4). Removal of a second electron from 1(+) or 2(+) leads to the dicationic species 1(2+) and 2(2+), which spontaneously lose a proton and produce the cationic metallabenzothiabenzene complexes [(triphos)M(eta(2)-C,S-C8H6S)](+) (M = Rh, 5(+); Ir, 7(+)). Finally, addition of one elecytron to 5(+) or 7(+) produces the corresponding neutral paramagnetic metallabenzothiabenzene complexes [(triphos)M(eta(2)-C,S-C8H6S)] (M = Rh, 5; Ir, 7). All the long-lived paramagnetic compounds have been characterized by X-band ESR spectroscopy.

  DOI：

  10.1021/om00009a049