(S)-η5-Cp(cobalt)(iodo)2(P(phenyl)2N(H)CH(methyl)phenyl) | 113109-08-3

• 英文名称: (S)-η5-Cp(cobalt)(iodo)2(P(phenyl)2N(H)CH(methyl)phenyl)
• 英文别名: (SC)-(η(5)-C5H5)CoI2(PPh2NHCH(Me)Ph)
• CAS: 113109-08-3
• 化学式: C₂₅H₂₅CoI₂NP
• 分子量: 683.256
• InChiKey: ULKCBFYCOVYVQG-UYVPJCOTSA-L

计算性质

• 辛醇/水分配系数(LogP)：
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• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为反应物：
  描述：

  (S)-η5-Cp(cobalt)(iodo)2(P(phenyl)2N(H)CH(methyl)phenyl) 、 (二乙基氨基)二甲氧基膦 以 苯 为溶剂， 以35.1%的产率得到(SCo, SP, SC)-(η(5)-C5H5)CoI(P(O)(NEt2)(OMe))(PPh2NHCH(Me)Ph)
  参考文献：
  名称：

  Yu, Yongfei; Jablonski, Chet; Bridson, John, Organometallics, 1997, vol. 16, p. 1270 - 1277

  摘要：

  DOI：
• 作为产物：
  描述：

  carbonyl(η-5-cyclopentadienyl)diiodocobalt(III) 、 (S)-(-)-N-diphenylphosphino-α-methylbenzylamine 以 苯 为溶剂， 以68%的产率得到(S)-η5-Cp(cobalt)(iodo)2(P(phenyl)2N(H)CH(methyl)phenyl)
  参考文献：
  名称：

  Brunner, Henri; Jablonski, Chet R.; Jones, Peter G., Organometallics, 1988, vol. 7, # 6, p. 1283 - 1292

  摘要：

  DOI：

文献信息

• Diastereoselective Arbuzov dealkylation and evidence for phosphorus-carbon bond activation of prochiral cobalt(III) phosphonite complexes
  作者：Brian J. Boone、Chet R. Jablonski、Peter G. Jones、Michael J. Newlands、Yongfei Yu

  DOI：10.1021/om00032a029

  日期：1993.8

  (S(c))-(eta5-CP)CoI2(PPh2NHC*H(Me)Ph) reacts with 1 equiv of dimethyl tert-butyl- or ethylphosphonite in methylene chloride solution to give diastereomeric 'P-chiral phosphinate Arbuzov products (R,S(Co),S(P);S(C))-(eta5-Cp)CoI(PPh2NHC*H(Me)Ph)(P(O)(OMe)(t-Bu)) (3a) and (R,S(Co),S(P);S(C))-(eta5-Cp)CoI(PPh2NHC*H(Me)Ph)(P(O)(OMe)(Et))(3b), respectively. Apparent phosphorus-carbon bond cleavage also occurs to give (R,S(Co);S(C))-(eta5-Cp)CoI(PPh2NHC*H(Me)-Ph)P(O)(OMe)2) (4), which was isolated in low yield after aerial workup. Two diastereomers of the tert-butyl series 3a and one diastereomer of the four isolated for the ethyl series 3b were characterized by single-crystal X-ray diffraction. (S(Co);R(P);S(C))-3a-1 crystallizes in the space group P2(1)2(1)2(1) with a = 9.815(4) angstrom, b = 14.314(6) angstrom, c = 21.120(9) angstrom, V = 2967(2) angstrom3, Z = 4, and RF = 2.83% for 5958 reflections (F > 4.0sigma(F)) at 198 K. (R(Co);S(P);S(C))-3a-2 crystallizes in the space group P2(1) with a = 13.073(5) angstrom, b = 8.731(2) angstrom, c = 13.537(5) angstrom, beta = 106.49(3)-degrees, V = 1481.5(9) angstrom3, Z = 2, and R(F) = 3.19 % for 4846 reflections (F > 4.0sigma(F)) at 198 K. (R(Co);S(P);S(C))-3b-2 crystallizes in the space group P2(1)2(1)2, with a = 8.7004(7) angstrom, b = 12.0769(18) angstrom, c = 27.490(3) angstrom, V = 2888.5(6) angstrom3, Z = 4, and R(F) = 4.4 % for 3118 reflections (F > 2.5sigma(F)) at 297 K. The absolute configurations of all diastereomers were assigned on the basis of crystallographic results, circular dichroism, and chemical cycles involving Co epimerization. P=O ... H-N intramolecular hydrogen bonding establishes a 'chaise longue'' conformation with pseudoaxial eta5-Cp and pseudoequatorial iodide in the solid state. Proton nuclear Overhauser difference (NOED) spectra show that the solid-state conformation is retained in solution. Optical yields increased with increasing steric demands of the prochiral phosphonite substituent. A model based on 1,3-diaxial steric interactions in the transition state leading to dealkylation is proposed to account for the observed Co --> P chiral induction.