| 1314325-02-4

• CAS: 1314325-02-4
• 化学式: C₂₅H₃₆ClO₃P₂Rh
• 分子量: 584.865
• InChiKey: IDGRNIUHOPIUHR-UHFFFAOYSA-M

反应信息

• 作为产物：
  描述：

  trans-Rh(Cl)(κ2-P,C-P(OC6H4)-(i-C3H7)2)(κ2-PC(acyl)-P(OC6H4CO)(i-C3H7)2) 以 甲苯 为溶剂， 生成
  参考文献：
  名称：

  Activation of an Unstrained C(sp²)–C(sp²) Single Bond Using Chelate-Bisphosphinite Rhodium(I) Complexes

  摘要：

  The reaction of [Rh(coe)(2)Cl](2) with the ligands P(Pr-i)(2)-O-Ph-pX-CO-Ph-pX-O-P(Pr-i)(2) (L1 X = H and L2 X = OMe) containing a benzophenone moiety resulted in the quantitative oxidative addition of the PhC-CO single bond under very mild conditions (193 K, 2a/b). For L2 the mechanism and the kinetics of the oxidative addition were investigated. Only complex 2a (X-ray crystal structure included) shows an exchange of the metal-bonded carbon moieties via migratory extrusion/insertion (3a) in solution. Thermodynamic parameters for this process were determined (for 3a -> 2a Delta H degrees = 9.3 +/- 0.5 kJ/mol, Delta S degrees = 53.8 +/- 1.8 J/(K mol)). The further fate, in particular the reductive elimination, of 2a/b was investigated and compared to the behavior of Ir. The reaction of 2a/b with several Lewis bases such as CO, (CO)-C-13, tert-butyl isonitrile, pyridine, acetonitrile, and N-15-acetonitrile was investigated. DFT calculations for the most important steps were performed.

  DOI：

  10.1021/om200288e