trans-[Re(CO)4I(PPh3)] | 142560-39-2

• 英文名称: trans-[Re(CO)4I(PPh3)]
• 英文别名: IRe(CO)4(ax-PPh3)；trans-[Re(PPh3)I(CO)4]
• CAS: 142560-39-2；15189-55-6
• 化学式: C₂₂H₁₅IO₄PRe
• 分子量: 687.444
• InChiKey: LYSUUGQXCAHDTJ-UHFFFAOYSA-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：
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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：

  trans-[Re(CO)4I(PPh3)] 以 四氯化碳 为溶剂， 生成 Re2(CO)8(PPh3)2
  参考文献：
  名称：

  XRe(CO)4L (X = Cl, I; L = CO, pip, PPh) 配合物的光物理研究。流体溶液中有机金属配合物的配体场发光示例

  摘要：

  一系列cis-XRe(CO)/sub 4/L (X = Cl, I; L = NC/sub 5/H/sub 11/ (pip), PPh/sub 3/) 配合物已通过光化学和母体 XRe(CO)/sub 5/ 物种的热反应。这些复合物在 293 K 的溶液和 80 K 的 EPA 玻璃中的电子吸收光谱已被记录。最低的吸收系统被明确指定为配体场 (LF) /sup 1/A/sub 1/(e/sup 4 /b/sub 2//sup 2/) ..-->.. /sup 1,3/(e/sup 3/b/sub 2//sup 2/a/sub 1//sup 1/) ; 能带能量取决于 L 并且按照 LF 强度排序为 CO > P 供体 > N 供体。来自 cis-XRe(CO)/sub 4/L (L = pip, PPh/sub 3/) 衍生物在 293 K 溶液和 EPA 玻璃中在 80 K 下与最低能量

  DOI：

  10.1021/ja00220a028
• 作为产物：
  描述：

  Re2(CO)8(PPh3)2 在 碘 作用下， 以 萘烷 为溶剂， 以50-75的产率得到trans-[Re(CO)4I(PPh3)]
  参考文献：
  名称：

  Kramer, Gary; Patterson, John; Poë, Anthony, Inorganic Chemistry, 1980, vol. 19, # 5, p. 1161 - 1169

  摘要：

  DOI：

文献信息

• Homogeneous CO Hydrogenation: Ligand Effects on the Lewis Acid-Assisted Reductive Coupling of Carbon Monoxide
  作者：Alexander J. M. Miller、Jay A. Labinger、John E. Bercaw

  DOI：10.1021/om100638d

  日期：2010.10.25

  crystallographically characterized. The reaction of [(Ph2P(CH2)2B(C8H14))2Re(CO)4]+ with [HPt(dmpe)2]+ takes place via a “hydride shuttle” mechanism, in which hydride is transferred from Pt to a pendent borane and thence to CO, rather than by direct hydride attack at CO. Addition of a second hydride in C6D5Cl at −40 °C affords an unusual anionic bis(carbene) complex, which converts to a C−C bonded product

  关于悬垂的路易斯酸在CO的还原偶联中的作用的结构功能研究已有报道。含有零个，一个或两个膦基配体（pH下为阳离子铼羰基配合物2 P（CH 2）Ñ B（C 8 ħ 14），Ñ = 1-3）与亲核氢化反应[HPT（DMPE）2 ] +，以减少[M-CO] +到M-CHO; 该步骤对路易斯酸相对不敏感，因为可以使用具有适当酸强度的侧链（内部）和外部硼烷。相反，是否发生第二次氢化物转移和C-C键形成步骤很大程度上取决于膦硼烷配体中P和B之间的碳原子数，以及配合物中的侧基酸数目：较短的连接链长度有利这样的还原偶联，而更长的链和外部硼烷则无效。晶体学上已经表征了许多不同的物种，它们包含部分还原的CO基团，其确切结构随膦硼烷配体的性质和数量而显着变化。[（Ph 2 P（CH 2）2 B（C 8H 14））2 [HPT（DMPe）2 ] +的Re（CO）4 ] +通过“氢化物穿梭”机理发生，其中氢化物从PT
• Reaction mechanisms of metal–metal bonded carbonyls. Part XI. Reactions of nonacarbonyl(triphenylphosphine)dirhenium and octacarbonylbis(triphenylphosphine)dirhenium
  作者：David G. DeWit、J. Paul Fawcett、Anthony Poë

  DOI：10.1039/dt9760000528

  日期：——

  different activation parameters from the reaction with triphenylphosphine and these reactions cannot, therefore, both go via simple rate-determining homolytic fission. Reaction of [Re2(CO)8(PPh3)2] with PPh3 leads to mononuclear carbonylphosphine products and is half order in [Re2(CO)8(PPh3)2]. This reaction most probably does go via reversible homolytic fission. Reactions with oxygen, nitrogen monoxide, and

  可逆反应的[再动力学2（CO）9（PPH 3）] + PPH 3 ⇌ [重2（CO）8（PPH 3）2 ] + CO的萘烷中进行了研究，在获得的每个方向和激活参数。动力学行为非常简单，并且与配体离解机理相一致。但是，这也与金属迁移和均裂裂变机制相一致。[Re 2（CO）9（PPh 3）]与一氧化碳的反应具有与与三苯膦的反应完全不同的活化参数，因此这些反应不能同时进行通过简单的速率确定同质裂变。[Re 2（CO）8（PPh 3）2 ]与PPh 3的反应产生单核羰基膦产物，并且在[Re 2（CO）8（PPh 3）2 ]中为半序。该反应很可能确实通过可逆的均质裂变进行。还描述了与氧气，一氧化氮和碘的反应。
• The PdO catalysed reaction between Re(CO)5X (X  Cl, Br, I) and L (L  Group 15 donor ligand). Synthesis of Re(CO)4LX
  作者：Ann E. Leins、Neil J. Coville

  DOI：10.1016/0022-328x(91)86314-g

  日期：1991.4

  Previously there has been no high yielding synthesis of Re(CO)4LX (L = Group 15 donor ligand, X = Cl, Br, I). We here show that the PdO-catalysed reaction between Re(CO)5X and L gives Re(CO)4LX in > 75% yield when L has a cone angle less than 150-degrees. The new complexes have been fully characterised by IR and H-1 NMR spectrscopy.
• Isomers of Re(CO)3(CNtBu)LX: Synthetic strategies starting from MnRe(CO)8(CNtBu)L and Re(CO)4LX (X  halogen; L Group 15 donor ligand)
  作者：Ann E. Leins、Neil J. Coville

  DOI：10.1016/0022-328x(94)87272-4

  日期：1994.1

  Reaction of Re(CO)(4)LX (L = PMePh(2), PMe(2)Ph, PPh(3), P(OMe)(3), P((OPr)-Pr-i)(3), P(O-o-tol)(3); X = Br,I) with (t)BuNC in the presence of PdO catalyst gave the new complexes Re(CO)(3)(CN(t)Bu)LX in high yield(> 60%). The new complexes were shown by spectroscopic techniques (IR, H-1 and P-31 NMR) to comprise a mixture of mer and fac isomers. The mer/fac ratio decreased with reaction temperatures (e.g. L = P(OMe)(3); 10 degrees C, ratio = 3; 45 degrees C, ratio = 0.25). At high temperatures (90 degrees C) isomerization of the mer to the fac isomers (L = PMe(2)Ph, P(OMe)(3)) occurred, suggesting that the mer isomer was the kinetic product of the catalyzed reaction. Reactions induced by Me(3)NO gave similar effects. Halogen cleavage of MnRe(CO)(8)(CN(t)Bu)L, prepared from MnRe(CO)(9)(CN(t)Bu) and L in the presence of Me(3)NO, yielded either one or two isomers of Re(CO)3(CN(t)Bu)(L)X (X = I, Br; 40% yield). For large L (e.g. PPh(3)) a new mer isomer with L trans to X was synthesized, and characterized by IR and NMR spectroscopy. For small L (e.g. P(OMe)(3)) a mixture of the two different mer products was obtained. The product isomer ratio was determined predominantly by the position of L in the starting dimer.
• Haupt, H.-J.; Balsaa, P.; Floerke, U., Zeitschrift fur Anorganische und Allgemeine Chemie
  作者：Haupt, H.-J.、Balsaa, P.、Floerke, U.

  DOI：——

  日期：——