(η(5)-C5H4Me)Re(CO)3

• 分子结构分类: 有机化合物 - 碳氢化合物 - 不饱和烃
• 英文名称: (η(5)-C5H4Me)Re(CO)3
• 化学式: C₉H₇O₃Re
• 分子量: 349.36
• InChiKey: MSNZEMLJGXSRLC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  13
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.11
• 拓扑面积：
  3
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (η(5)-C5H4Me)Re(CO)3 以 正己烷 为溶剂， 生成
  参考文献：
  名称：

  Lewis, Larry N.; Caulton, Kenneth G., Inorganic Chemistry, 1981, vol. 20, # 4, p. 1139 - 1142

  摘要：

  DOI：
• 作为产物：
  描述：

  以 not given 为溶剂， 生成 (η(5)-C5H4Me)Re(CO)3
  参考文献：
  名称：

  Lewis, Larry N.; Caulton, Kenneth G., Inorganic Chemistry, 1981, vol. 20, # 4, p. 1139 - 1142

  摘要：

  DOI：

文献信息

• Structure and dynamics of the η2-hexafluorobenzene complexes [Re(η5-C5H4R)(CO) 2(η2-C6F6)] (R = H or Me) and [Rh(η5-C5Me5)(PMe3)( η2-C6F6)]
  作者：Catherine L. Higgitt、A. Hugo Klahn、Madeleine H. Moore、Beatriz Oelckers、Martin G. Partridge、Robin N. Perutz

  DOI：10.1039/a608135e

  日期：——

  Photolysis of [Re(η 5 -C 5 H 4 R)(CO) 3 ] (R = H or Me) in hexafluorobenzene yielded [Re(η 5 -C 5 H 4 R)(CO) 2 ( η 2 -C 6 F 6 )] containing the η 2 -co-ordinated arene. The complex containing η 5 -C 5 H 5 has been characterised crystallographically. It forms monoclinic crystals in space group P2 1 /n with Z = 4, a = 7.926(2), b = 12.179(4), c = 13.675(4) Å and β = 102.91(2)°. The structure reveals the expected features of distortion of the C 6 F 6 unit from planarity at the co-ordinated C–C bond. The rhenium lies 2.059(7) Å from the mid-point of the co-ordinated C–C bond of C 6 F 6 . The IR and low-temperature 19 F NMR spectra reveal the presence of two rotamers, which are interconverted by rotation about the metal–C 6 F 6 bond with ΔG ‡ = 36.7 kJ mol -1 at 184 K. At higher temperatures a second intramolecular rearrangement causes broadening of the 19 F resonances. This fluxional process has been identified as a [1, 2]-shift of the site of rhenium co-ordination by linewidth and exchange spectroscopy measurements: ΔH ‡ = 57.6 ± 0.5 kJ mol -1 , ΔS ‡ = -7 ± 2 J K -1 mol -1 . The dynamic behaviour of the (η 5 -C 5 H 4 Me) complex is extremely similar. The crystal structure of [Rh(η 5 -C 5 Me 5 )(PMe 3 )( η 2 -C 6 F 6 )], synthesised previously, has been determined for comparison. It crystallises in the same space group with a = 8.694(9), b = 16.818(9), c = 14.642(6) Å and β = 106.69(6)°. The structural features of this rhodium complex are very similar to the rhenium complex, but the metal lies 1.920(5) Å from the mid-point of the co-ordinated C–C bond of the C 6 F 6 unit. The shortening of the M–C 6 F 6 bond is associated with the stereochemical rigidity of this complex. The C–F bonds of the co-ordinated carbons atoms are 0.049(7) Å longer than the remaining C–F bonds. Comparison of structural features of three η 2 -C 6 F 6 complexes revealed that the distortions of the C 6 F 6 unit are almost constant, indicating a hard potential-energy surface. The analogy to co-ordinated C 2 F 4 is reinforced by the similarity in co-ordination geometry. The electron-withdrawing character of η 2 -C 6 F 6 is confirmed by the (CO) frequencies of [Re(η 5 -C 5 H 5 )(CO) 2 (η 2 -C 6 F 6 )] which lie at the high limit for complexes of the type [Re(η 5 -C 5 H 5 )(CO) 2 L].

  Re(Î- 5 -C 5 H 4 R)(CO) 3 ]（R = H 或 Me）在六氟苯中光解后得到了含有 Î- 2 共配位炔的 [Re(Î- 5 -C 5 H 4 R)(CO) 2 ( Î- 2 -C 6 F 6 )] 复合物。含有 Î- 5 -C 5 H 5 的复合物已经过晶体学鉴定。它在空间群 P2 1 /n 中形成单斜晶体，Z = 4，a = 7.926(2)，b = 12.179(4)，c = 13.675(4)，δ = 102.91(2)°。该结构揭示了 C 6 F 6 单元在共线 CâC 键处平面变形的预期特征。铼位于 C 6 F 6 配位 CâC 键中点的 2.059(7) à 处。红外光谱和低温 19 F NMR 光谱显示了两个旋转体的存在，它们在 184 K 时通过围绕金属与 C 6 F 6 键的旋转而相互转化，δG ¡ = 36.7 kJ mol -1 。通过线宽和交换光谱测量，这一通量过程被确定为铼配位位点的[1, 2]位移：δH ＝ 57.6 ± 0.5 kJ mol -1 ，δS ＝ -7 ± 2 J K -1 mol -1 。 (δ- 5 -C 5 H 4 Me) 复合物的动态行为极为相似。之前合成的[Rh(δ- 5 -C 5 Me 5 )(PMe 3 )( δ- 2 -C 6 F 6 )]的晶体结构已经确定，以便进行比较。它在相同的空间群中结晶，a = 8.694(9)，b = 16.818(9)，c = 14.642(6) à 和 δ = 106.69(6)° 。该铑络合物的结构特征与铼络合物十分相似，但金属距离 C 6 F 6 单元共价 CâC 键的中点有 1.920(5) Ã。MâC 6 F 6 键的缩短与该复合物的立体化学刚性有关。共配位碳原子的 CâF 键比其余的 CâF 键长 0.049(7) Ã。对三种δ- 2 -C 6 F 6 复合物的结构特征进行比较后发现，C 6 F 6 单元的畸变几乎是恒定的，这表明该复合物具有坚硬的势能面。配位几何的相似性加强了与配位 C 2 F 4 的相似性。Re(Î- 5 -C 5 H 5 )(CO) 2 (Î- 2 -C 6 F 6 )] 的（CO）频率位于[Re(Î- 5 -C 5 H 5 )(CO) 2 L]类型络合物的高限，这证实了δ- 2 -C 6 F 6 的吸电子特性。
• Solid-State Photochemical <i>diag</i><i>−</i><i>lat </i>Isomerization of (η⁵-C₅H₄R)Re(CO)(L)X₂ on the Surface of Silica Gel
  作者：Lin Cheng、Neil J. Coville

  DOI：10.1021/om960726x

  日期：1997.2.1

  I) adsorbed on silica gel results in isomerization of the complexes into the corresponding lateral isomers in good yield (typically >80%). For L = CO, the isomerization reactions occurred in the direction reverse to that found in solution in which lat-to-diag isomerization was observed. It was found that the ratio of diagonal to lateral isomers established on the surface of silica gel was influenced

  的室温可见照明（200W光源）DIAG - （η 5 -C 5 H ^ 4 R）的Re（CO）（L）X 2（R = H，烷基; L = CO，P（OR）3 ; X = Br，I）吸附在硅胶上导致配合物异构化为相应的侧向异构体，收率良好（通常> 80％）。对于L = CO，异构化反应发生在相反的方向上所发现在其中溶液纬度-到-诊断观察到异构化。发现在硅胶表面上建立的对角异构体与侧向异构体的比率受X和L的影响，即。（η 5 -C 5 H ^4 Me）中的Re（CO）[P（OR）3 ]溴2 >（η 5 -C 5 H ^ 4 Me）中的Re（CO）2溴2 >（η 5 -C 5 H ^ 4 Me）中的Re（CO）2我2。用Me 2 SiCl 2化学除去表面羟基表明，仅化学吸附在硅胶表面上的a配合物的单层经历了异构化。描述了使二氧化硅表面羟基的作用合理化的机理。
• Organometallic Synthesis as a Continuous Process:  The Synthesis and Isolation of Cr(CO)₅(η²-C₃H₆) and (C₅R₅)Mn(CO)₂(η²-C₃H₆) (R = H and Me) from Superheated Liquid Propene
  作者：Jennifer L. King、Karine Molvinger、Martyn Poliakoff

  DOI：10.1021/om0000717

  日期：2000.11.1

  (C5R5)Mn(CO)2(η2-C3H6) (R = H and Me) and Cr(CO)5(η2-C3H6) have been synthesized by UV photolysis of CpMn(CO)3 and Cr(CO)6 in liquid propene at 25 °C and 2100 psi pressure and by the thermal reaction of Cp*Mn(CO)2(EVE) (EVE = ethyl vinyl ether) with propene. The propene complexes are precipitated by rapid expansion through a back pressure regulator. The precipitation leads to finely divided solid materials

  （C 5 - [R 5）的Mn（CO）2（η 2 -C 3 H ^ 6）（R = H和Me）和Cr（CO）5（η 2 -C 3 H ^ 6）已经由太平洋地磁观测网的紫外光解合成25°C和2100 psi压力下液态丙烯中的（CO）3和Cr（CO）6以及Cp * Mn（CO）2的热反应（EVE）（EVE =乙基乙烯基醚）与丙烯。丙烯配合物通过背压调节器快速膨胀而沉淀。沉淀导致细碎的固体物质。尽管这些化合物包含一些残留的起始原料，但以前没有一种化合物以固体形式分离出来。所有三种化合物在固态中比在溶液中稳定得多。Cp *络合物的热稳定性似乎不如Cp类似物。
• Organometallic flow chemistry: <i>solvento</i> complexes
  作者：Benjamin J. Frogley、Anthony F. Hill、Hideki Onagi、Lachlan J. Watson

  DOI：10.1039/d2dt02583c

  日期：——

  synthetically versatile and labile solvento complexes [Ln}M(CO)x−1(THF)], thereby obviating many of the caveats associated with photochemical syntheses using either ‘batch’ or falling film techniques. Conversions were optimised and yields assayed by a combination of in situ infrared spectroscopy and derivatisation as the corresponding triphenylphosphine complexes [Ln}M(CO)x−1(PPh3)].

  金属羰基化合物 [L n }M(CO) x ] [L n }M(CO) x = Cr(CO) 6 , Mo(CO) 6 , W(CO) 6 , Mn( CO) 3 (η-C 5 H 4 Me), Re(CO) 3 (η-C 5 H 5 )] 在四氢呋喃 (THF) 中方便地提供合成通用且不稳定的溶剂络合物 [L n }M(CO) x -1(THF)]，从而避免了许多与使用“批量”或降膜技术的光化学合成相关的警告。通过结合原位红外光谱和衍生化作为相应的三苯基膦络合物 [L n }M(CO) x -1 (PPh 3 )]，优化了转化率并测定了产率。
• Gmelin Handbuch der Anorganischen Chemie, Gmelin Handbook: Sn: Org.Verb.2, 1.1.2.1.9, page 93 - 108
  作者：

  DOI：——

  日期：——