| 121987-66-4

• CAS: 121987-66-4
• 化学式: CF₃O₃S*C₁₆H₂₁MoO₃
• 分子量: 506.351
• InChiKey: NCWBUIGIJJKUDP-PRBGOWCYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 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：
  None
• 氢给体数：
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• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  在 三乙胺 作用下， 以 二氯甲烷 为溶剂， 生成 {Mo(exo-anti-η3-1-C3H4CHO)(CO)2(η-5-C5Me5)}
  参考文献：
  名称：

  Benyunes, Stephen A.; Green, Michael; Grimshire, Michael J., Organometallics, 1989, vol. 8, # 9, p. 2268 - 2270

  摘要：

  DOI：
• 作为产物：
  描述：

  {Mo(exo-anti-η3-1-C3H4CHO)(CO)2(η-5-C5Me5)} 、 三氟甲磺酸 以 二氯甲烷 为溶剂， 生成
  参考文献：
  名称：

  Benyunes, Stephen A.; Green, Michael; Grimshire, Michael J., Organometallics, 1989, vol. 8, # 9, p. 2268 - 2270

  摘要：

  DOI：

文献信息

• Reactions of co-ordinated ligands. Part 50. The synthesis of functionalised η³-allyl complexes of molybdenum and their conversion into η⁴-s-trans-1,3-dienes
  作者：Stephen A. Benyunes、Alessandra Binelli、Michael Green、Michael J. Grimshire

  DOI：10.1039/dt9910000895

  日期：——

  Reaction of the labile bis(acetonitrile) complexes [Mo(NCMe)2(CO)2(eta-5-L)][BF4] (L = C9H7 1 or C5Me5 2) with the 1-trimethylsilyloxybuta-1,3-dienes Me3SiOCH = CR1CH = CHR2 (R1 = R2 = H; R1 = Me, R2 = H; R1 = H, R2 = Me) results in initial co-ordination of the diene followed by a rapid desilylation affording the 4-oxo-functionalised allyls [Mo(eta-3-CR2R3CHCR1CHO)(CO)2(eta-5-L)] 4 and 6-9. Complexes 4 and 6-9 are generated in the form of isomeric mixtures, arising through syn-anti isomerism at C2 of the allyl ligand together with the presence of non-interconvertible exo and endo orientations for the latter with respect to the metal fragment. Addition of Ph3P = CH2 to 6 (R1 = R2 = R3 = H) and 7 (R1 = Me, R2 = R3 = H) effects smooth conversion into the eta-3-pentadienyl complexes [Mo(eta-3-CR2R3CHCR1CHCH2)(CO)2(eta-5-C5Me5)] 11 (R1 = R2 = R3 = H) and 12 (R1 = Me, R2 = R3 = H). The low-temperature (-78-degrees-C) protonation of compounds syn-6-8 using CF3SO3H results in a quantitative transformation into the s-trans-diene cations [Mo(eta-4-s-trans-trans-HOCHCR1CHCR2R3)-(CO)2(eta-5-C5Me5)][CF3SO3] 13 (R1 = R2 = R3 = H), 14 (R1 = Me, R2 = R3 H) and 15 (R1 = R3 = H, R2 = Me), characterised in situ by H-1 NMR spectroscopy. Above -30-degrees-C, 13-15 undergo an irreversible rearrangement in solution to the corresponding s-cis diene cations. Deprotonation of 13-15 by treatment with NEt3 regenerates the syn isomers of 6-8, whilst the s-cis diene cations produce only the anti species under the same conditions. These results are interpreted in terms of an overall retention of stereochemistry of the C4 ligand throughout these manipulations. The eta-3-pentadienyl complexes 11 and 12 undergo analogous transformations upon addition of CF3SO3H producing the thermally unstable s-trans-diene cations [Mo(eta-4-s-trans-trans-MeCHCRCHCH2)(CO)2(eta-5-C5Me5)][CF3SO3] 16 (R = H) and 17 (R = Me), which are likewise converted into their s-cis isomers at temperatures in excess of -20-degrees-C.