S(Co),S(C)-{η5-CpCo(CF3)(PPh2NHCH(Me)Ph)(PO(OMe)2)} | 142260-87-5

• 英文名称: S(Co),S(C)-{η5-CpCo(CF3)(PPh2NHCH(Me)Ph)(PO(OMe)2)}
• CAS: 142260-87-5
• 化学式: C₂₈H₃₁CoF₃NO₃P₂
• 分子量: 607.495
• InChiKey: OHJXTQMGKRDKRW-UYVPJCOTSA-N

反应信息

• 作为产物：
  描述：

  R,S(Co),S(C)-{η5-CpCo(CF3)(PPh2NHCH(Me)Ph)(I)} 、 三甲氧基磷 以 苯 为溶剂， 以27.2%的产率得到R(Co),S(C)-{η5-CpCo(CF3)(PPh2NHCH(Me)Ph)(PO(OMe)2)}
  参考文献：
  名称：

  Synthesis, structure, and absolute configuration of chiral, pseudooctahedral perfluoroalkyl-substituted dimethylphosphonate complexes

  摘要：

  The substitution-labile complexes eta-5-CpCo(X)(PPh2N(R)C*H(Me)Ph)(I), 6(ab)(alpha,beta), react with trimethyl phosphite to afford eta-5-CpCo(X)(PPh2N(R)C*H(Me)Ph)(P(O)(OMe)2), 7(a,b)alpha, and eta-5-CPCO(X)(P(OMe)3)(I), 8a,b (a, X = CF3; b, X = n-C3F7; alpha, R = H; beta, R = Me). Arbuzov dealkylation to give 7 occurs.only for R = H and requires intramolecular P=O...H-N hydrogen bonding, which develops early in the transition state to "anchor" the aminophosphine ligand. The chiral, Co-epimeric Arbuzov products were separated and characterized. The absolute configuration of (+)436-7b-alpha was determined crystallographically. (+)436-7b-alpha crystallizes in the monoclinic system P2(1) with a = 11.0941 (20) angstrom, b = 16.9200 (22) angstrom, c = 16.927 (3) angstrom, beta = 91.241 (15)-degrees, V = 3176.6 (9) angstrom3, Z = 4, and R(f) = 8.4% (R(w) = 5.1%) for 1638 reflections with I > 2.5-sigma-I and was found to contain two independent molecules in the asymmetric unit. Absolute configurations of (-)436-7b-alpha, (-)436-7a-alpha, and (+)436-7a-alpha were assigned on the basis of chiroptical evidence. P=O...H-N hydrogen bonding establishes a pseudoboat conformation with pseudoaxial eta-5-Cp and pseudoequatorial n-C3F7 in the solid state. Nuclear Overhauser difference (NOED) spectra show that the solid-state conformation persists in solution.

  DOI：

  10.1021/om00044a018