fac-Re(CO)3(PMe3)2(OSO2CF3) | 138695-27-9

• 英文名称: fac-Re(CO)3(PMe3)2(OSO2CF3)
• CAS: 138695-27-9
• 化学式: C₁₀H₁₈F₃O₆P₂ReS
• 分子量: 571.465
• InChiKey: ICDLNSBTZCWFOJ-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  fac-Re(CO)3(PMe3)2(OSO2CF3) 在 sodium 、 CH₃OH 作用下， 以 苯 为溶剂， 以86%的产率得到
  参考文献：
  名称：

  醇盐和芳基氧化物配合物的合成，结构和交换反应。质子和氢原子在交换过渡态中转移的证据

  摘要：

  A series of rhenium(I) aryloxide and alkoxide complexes have been prepared. The aryloxide complexes may be prepared by treatment of the methyl complex (CO)3(PPh3)2ReCH3 (1) with p-cresol, affording (CO)3(PPh3)2ReOC6H4CH3 (3a). The PPh3 ligands may be displaced by a number of other ligands (PMe3,1,2-(dimethylarsino)benzene (diars), or t-BuNC), providing a route to substituted cresolate complexes. Alkoxide complexes of the type (CO)3(L)2ReOR (R = CH3 (6), CH2CH3 (7), CH(CH3)3 (8); L, L2 = PMe3, diars, depe, or (S,S)-bdpp) may be prepared by treatment of the triflate complexes (CO)3(L)2ReOSO2CF3 with the sodium salt of the appropriate alcohol. These alkoxide complexes are quite stable and do not decompose by beta-hydride elimination. The coordinated alkoxide ligands exchange rapidly with added alcohols in solution, while the exchange of aryloxide ligands with added phenols is much slower. The alkoxide complexes may be converted into the aryloxide complexes by addition of the desired phenol and heating to 44-degrees-C. This reaction proceeds via the intermediacy of a hydrogen-bonded adduct formed by coordination of the phenol O-H proton to the alkoxide oxygen atom. The hydrogen bonds are quite strong, and the adducts may be isolated if desired. One of the hydrogen-bonded adducts of 7e and p-cresol, (CO)3(depe)ReOCH2CH3...HOCrH4CH3, has been structurally characterized. The O-O distance is 2.532(5) angstrom, a value commonly observed for strong hydrogen bonds. The rates of conversion of a series of these complexes (CO)3(diars)ReOCH3...HOC6H4X (6b...HOC6H4X) to (CO)3(diars)ReOC6H4X (3b) and methanol were studied. The rate of this reaction was found to be cleanly first order in the hydrogen-bonded complex 6b...HOC6H4X and was unaffected by the addition of excess phenol and added bases. The rate was found to increase when the substituent X either lowers the O-H bond dissociation energy or increases the acidity of the phenol, indicating that the transition state for this reaction can have either proton or hydrogen atom transfer character.

  DOI：

  10.1021/om00027a031
• 作为产物：
  描述：

  fac-(η(1)-C5H5)Re(CO)3(PMe3)2 、 三氟甲磺酸 以 二氯甲烷 为溶剂， 以50%的产率得到fac-Re(CO)3(PMe3)2(OSO2CF3)
  参考文献：
  名称：

  醇盐和芳基氧化物配合物的合成，结构和交换反应。质子和氢原子在交换过渡态中转移的证据

  摘要：

  A series of rhenium(I) aryloxide and alkoxide complexes have been prepared. The aryloxide complexes may be prepared by treatment of the methyl complex (CO)3(PPh3)2ReCH3 (1) with p-cresol, affording (CO)3(PPh3)2ReOC6H4CH3 (3a). The PPh3 ligands may be displaced by a number of other ligands (PMe3,1,2-(dimethylarsino)benzene (diars), or t-BuNC), providing a route to substituted cresolate complexes. Alkoxide complexes of the type (CO)3(L)2ReOR (R = CH3 (6), CH2CH3 (7), CH(CH3)3 (8); L, L2 = PMe3, diars, depe, or (S,S)-bdpp) may be prepared by treatment of the triflate complexes (CO)3(L)2ReOSO2CF3 with the sodium salt of the appropriate alcohol. These alkoxide complexes are quite stable and do not decompose by beta-hydride elimination. The coordinated alkoxide ligands exchange rapidly with added alcohols in solution, while the exchange of aryloxide ligands with added phenols is much slower. The alkoxide complexes may be converted into the aryloxide complexes by addition of the desired phenol and heating to 44-degrees-C. This reaction proceeds via the intermediacy of a hydrogen-bonded adduct formed by coordination of the phenol O-H proton to the alkoxide oxygen atom. The hydrogen bonds are quite strong, and the adducts may be isolated if desired. One of the hydrogen-bonded adducts of 7e and p-cresol, (CO)3(depe)ReOCH2CH3...HOCrH4CH3, has been structurally characterized. The O-O distance is 2.532(5) angstrom, a value commonly observed for strong hydrogen bonds. The rates of conversion of a series of these complexes (CO)3(diars)ReOCH3...HOC6H4X (6b...HOC6H4X) to (CO)3(diars)ReOC6H4X (3b) and methanol were studied. The rate of this reaction was found to be cleanly first order in the hydrogen-bonded complex 6b...HOC6H4X and was unaffected by the addition of excess phenol and added bases. The rate was found to increase when the substituent X either lowers the O-H bond dissociation energy or increases the acidity of the phenol, indicating that the transition state for this reaction can have either proton or hydrogen atom transfer character.

  DOI：

  10.1021/om00027a031

文献信息

• Oligophosphan-Liganden XLII. Carbonyl(cyclopentadienyl)rhenium(I)-Komplexe η1-C5H5Re(CO)3L2 mit fluktuierender sp3- und starrer sp2-Koordination des C5H5-Rings
  作者：Lutz Dahlenburg、Gabriele Hillmann、Markus Ernst、Matthias Moll、Falk Knoch

  DOI：10.1016/s0022-328x(96)06503-5

  日期：1996.11

  allowed to interact with Na[Ca5H5] in THF. Treatment of 18 with Na[C5H5] produced fac-η1-C5H5Re(CO)3[C5H8(PCy2)2] as a mixture of three isomers with the rhenium atom in the allylic position of a fluxional sp3-bonded ring (25a) or in the two vinylic sites of an sp2-bonded rigid C5H5 sytem, where the CH2 group is either α or β to the metalated carbon atom (25b, 25c), η5-C5H5Re(CO)3 and fac-[Re(CO)3(Ph2PCH2PPh2-P

  卤rh（I）配合物的混合物fac-Re（CO）3 L 2 X（L / X = PMe 3 / Br（1），PPh 3 / Cl（2）PCy 3 / Br（3）），fac- Re（CO）3（Ph 2 PCH 2 PPh 2）Br，4 fac-Re（CO）3 [R 2 P（CH 2）2 PR 2 ] Br（RMe（5），Ph（6），Cy （7）），fac-Re（CO）3 [Ph 2 P（CH 2）3 PPh2 ] Cl，8和fac-Re（CO）3 [C 5 H 8（PCy 2）2 ] Br，9（C 5 H 8（PCy 2）2 = rac，反式-环戊烷-1,2-二基-双（二环己基）膦）与Ag [O 3 SCF 3 ]生成fac-Re（CO）3（PR 3）2 OSO 2 CF 3（RMe（10），Ph（11），Cy（12） ），fac-Re（CO）3 [R 2P（CH 2）n PR 2 ] OSO
• Simpson, Robert D.; Bergman, Robert G., Organometallics, 1992, vol. 11, # 12, p. 3980 - 3993
  作者：Simpson, Robert D.、Bergman, Robert G.

  DOI：——

  日期：——