[6-(oxomethylidene)cyclohexa-2,4-dien-1-yl]-diphenyl-[tris(oxomethylidene)-λ⁷-chloranyl]phosphanium,rhenium | 15189-56-7

• 英文名称: [6-(oxomethylidene)cyclohexa-2,4-dien-1-yl]-diphenyl-[tris(oxomethylidene)-λ⁷-chloranyl]phosphanium,rhenium
• 英文别名: Re(CO)₄(PPh₃)Cl；ReCl(CO)4(PPh3)；cis-[Re(CO)4(PPh3)Cl]；cis-ClRe(CO)4(PPh3)；cis-Re(CO)4(PPh3)Cl
• CAS: 15189-56-7；18223-84-2；89577-17-3
• 化学式: C₂₂H₁₅ClO₄PRe
• 分子量: 595.992
• InChiKey: PQZSWJKAXBVLPU-UHFFFAOYSA-M

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：

  [6-(oxomethylidene)cyclohexa-2,4-dien-1-yl]-diphenyl-[tris(oxomethylidene)-λ⁷-chloranyl]phosphanium,rhenium 以0%的产率得到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 以 氯仿 为溶剂， 生成 [6-(oxomethylidene)cyclohexa-2,4-dien-1-yl]-diphenyl-[tris(oxomethylidene)-λ⁷-chloranyl]phosphanium,rhenium
  参考文献：
  名称：

  The use of SO2Cl2 in organometallic chemistry. Convenient high yield syntheses of [Fe(η-C5H5)(CO)3] [FeCl4] and [M(CO5Cl] (M = Mn or Re)

  摘要：

  DOI：

  10.1016/0022-328x(83)87170-8
• 作为试剂：
  描述：

  (E)-1-bromo-4-phenylbut-3-en-2-one 在 [6-(oxomethylidene)cyclohexa-2,4-dien-1-yl]-diphenyl-[tris(oxomethylidene)-λ⁷-chloranyl]phosphanium,rhenium 、 potassium carbonate 、 三乙胺 作用下， 以 二氯甲烷 、 甲苯 、 乙腈 为溶剂， 反应 10.0h， 生成 (1R*,5S*,6S*)-8-triisopropylsiloxy-2-(p-methoxybenzenesulfonyl)-6-phenyl-2-azabicyclo[3.3.0]octa-3,7-diene 、 (1R*,5S*,6R*)-8-triisopropylsiloxy-2-(p-methoxybenzenesulfonyl)-6-phenyl-2-azabicyclo[3.3.0]octa-3,7-diene 、 (2R*,5S*)-1-(p-methoxybenzenesulfonyl)-5-phenyl-2-(propa-1,2-dien-1-yl)-3-triisopropylsilyloxy-2,5-dihydro-1H-pyrrole 、 (2R*,5R*)-1-(p-methoxybenzenesulfonyl)-5-phenyl-2-(propa-1,2-dien-1-yl)-3-triisopropylsilyloxy-2,5-dihydro-1H-pyrrole
  参考文献：
  名称：

  基于炔烃双键碳官能化的钨（0）和hen（I）催化的乙二烯二烯丙基甲硅烷基醚串联环化反应

  摘要：

  报道了基于炔烃双碳官能化概念的炔属二烯醇甲硅烷基醚的钨（0）和rh（I）催化反应。在光辐照条件下用催化量的[W（CO）6 ]或[ReCl（CO）5 ]处理3-甲硅烷氧基-1,3-二烯-7-炔烃可合成合成有用的双环[3.3.0]辛烷衍生物产量。noted（I）配合物的催化活性极高。该反应已扩展至在其系链中包含氮原子的底物。在这种情况下，有两种合成上有用的杂环化合物：2-氮杂双环[3.3.0]辛烷衍生物9和单环二氢吡咯10获得具有烯丙基取代基的化合物，并且可以通过使用氮取代基和the（I）催化剂类型的适当组合来选择性地制备任何一种产物。该2-氮杂双环[3.3.0]辛烷衍生物9分别由执行处理N个选择性地得到在存在Ns个衍生物[RECL（CO）4（PPH 3）]，而二氢吡咯衍生物10通过处理而获得ñ  Mbs的衍生物与[RECL（CO）5 ] / AgSbF 6。最后，我们将此双碳官能化技术应

  DOI：

  10.1002/chem.201003019

文献信息

• Surface organometallic chemistry — Carbonyl complexes of Re(I) with silanolates as models of silica anchored rhenium carbonyl species
  作者：Giuseppe D'Alfonso、Claudia Dragonetti、Simona Galli、Elena Lucenti、Piero Macchi、Dominique Roberto、Renato Ugo

  DOI：10.1139/v05-104

  日期：2005.6.1

  Reaction of Me₃SiONa with [Re(CO)₅Cl] affords the new complex Na[Re₂(CO)₆(µ-OSiMe₃)₃], which could be generated via formation of [Re(CO)₅OSiMe₃] followed by immediate reaction with Me₃SiO^–. Substitution of some CO ligands by phosphines significantly decreases the electrophilicity of the Re(I) center, and therefore hinders further attack by Me₃SiO^–. Thus, fac-[Re(CO)₃(Ph₂PCH₂CH₂PPh₂)OTf] (OTf is the triflate anion) reacts with Me₃SiONa to give fac-[Re(CO)₃(Ph₂PCH₂CH₂PPh₂)OSiMe₃], a molecular model of silica anchored [Re(CO)₅OSi≡]. However, substitution of only one CO by triphenylphosphine is not enough to avoid the formation of [Re₂(CO)₆(µ-OSiMe₃)₃]^–. While fac-[Re(CO)₃(Ph₂PCH₂CH₂PPh₂)OSiMe₃] is stable towards hydrolysis, [Re₂(CO)₆(µ-OSiMe₃)₃]^– is readily hydrolyzed to [Re₂(CO)₆(µ-OH)(µ-OSiMe₃)₂]^–, a molecular model of silica anchored [Re₂(CO)₆(µ-OH)(µ-OSi≡)₂]^–, whose structure has been determined by single crystal X-ray diffraction. Key words: surface organometallic chemistry, rhenium, silica, silanolate, molecular model.

  Me₃SiONa与[Re(CO)₅Cl]的反应产生了新的配合物Na[Re₂(CO)₆(µ-OSiMe₃)₃]，该配合物可以通过生成[Re(CO)₅OSiMe₃]，然后立即与Me₃SiO^–反应来生成。 通过磷化物取代一些CO配体显著降低了Re(I)中心的亲电性，从而阻碍了Me₃SiO^–的进一步攻击。 因此，fac-[Re(CO)₃(Ph₂PCH₂CH₂PPh₂)OTf]（OTf是三氟甲磺酸根离子）与Me₃SiONa反应，得到fac-[Re(CO)₃(Ph₂PCH₂CH₂PPh₂)OSiMe₃]，这是硅氧化物锚定的[Re(CO)₅OSi≡]的分子模型。 然而，仅用三苯基膦取代一个CO并不足以避免形成[Re₂(CO)₆(µ-OSiMe₃)₃]^–。 虽然fac-[Re(CO)₃(Ph₂PCH₂CH₂PPh₂)OSiMe₃]对水解稳定，但[Re₂(CO)₆(µ-OSiMe₃)₃]^–很容易水解为[Re₂(CO)₆(µ-OH)(µ-OSiMe₃)₂]^–，这是硅氧化物锚定的[Re₂(CO)₆(µ-OH)(µ-OSi≡)₂]^–的分子模型，其结构已通过单晶X射线衍射确定。 关键词：表面有机金属化学，铼，硅，硅醇酸盐，分子模型。
• Associative substitution reactions of ·Re(CO)₅
  作者：Arnold Fox、John Malito、Anthony Poë

  DOI：10.1039/c39810001052

  日期：——

  Studies of competition between substitution and chlorine abstraction reactions of photochemically generated ·Re(CO)5 radicals show that substitution proceeds via a second-order associative path and not via CO dissociation.

  对光化学生成的·Re（CO）5自由基的取代和氯提取反应之间竞争的研究表明，取代是通过二阶缔合途径而不是通过CO分解进行的。
• The halogenation of toluene with sulphuryl chloride and dichlorine in the presence of transition metal complexes
  作者：Reg Davis、Jim L.A. Durrant、Christopher C. Rowland

  DOI：10.1016/0022-328x(86)80417-x

  日期：1986.11
• Rhenium carbonyls containing pyridyl ligands incorporating an alkyne entity
  作者：Jiann T. Lin、Shih-Sheng Sun、Jiann Jung Wu、Yen-Chywan Liaw、Kuan-Jiuh Lin

  DOI：10.1016/0022-328x(96)06167-0

  日期：1996.6

  Reactions of pyridyl ligands, 4,4'-dipyridylbutadiyne (DPB), 1,4-bis(4'-pyridylethynyl)benzene (BPEB), ferrocenyl-4-pyridylacetylene (FPA), 4-nitrophenyl-4'-pyridylacetylene (NPPA) and 4-aminophenyl-4'-pyridylacetylene (APPA), with Re(CO)(5)X (X = Cl,Br), cis-Re(CO)(4)(L)Cl (L = PPh(3), P(OMe)(3)), and [Re(CO)(3)(2,2'-bipy)(MeCN)][PF6], provides fac-Re(CO)(3)(eta(1)-DPB)(2)Cl (1), fac-Re(CO)(3)(PY)(2)Br (2, PY = FPA; 3, L = NPPA; 4, L = APPA), [fac-Re(CO)(3)(PPh(3))Cl](2)(mu-PY) (5, PY = BPEB; 6, PY = DPB), [fac-Re(CO)(3)(P(OMe)(3))Cl](2)(mu-DPB) (7), fac-Re(CO)(3)(PPh(3))(PY)Cl (8, PY = NPPA; 9, PY = FPA), [fac-Re(CO)(3)(2,2'-bipy)(PY)][PF6] (10, PY = NPPA; 11, PY = APPA; 12, PY = FPA), and [(fac-Re(CO)(3)(2,2'-bipy)}(2)(mu-PY)][PF6](2) (13, PY = DPB; 14, PY = BPEB). The energy of the metal to pyridyl pi* charge-transfer (MLCT) is investigated by electronic absorption spectra and cyclic voltammetry, X-ray structural analyses for 2 . CH2Cl2 and 12 . 2H(2)O were carried out. 2 . CH2Cl2:C12H28BrClN2O3P2Fe2Re; monoclinic; P2(1)/n, Z = 4; a = 15.188(2), b = 15.100(2), c = 16.254(1) Angstrom; beta = 102.22(1)degrees; R = 0.047; Rw = 0.040. 12 . 2H(2)O: C30H21F6N3O3PFeRe; monoclinic; P2(1)/n, Z = 4; a = 19.022(4), b = 9.339(2), c = 21.111(3) Angstrom; beta = 116.156(9)degrees; R = 0.043; Rw = 0.061.
• Rhenium Complexes with Weakly Coordinating Solvent Ligands, <i>cis</i>-[Re(PR₃)(CO)₄(L)][BAr_F], L = CH₂Cl₂, Et₂O, NC₅F₅:  Decomposition to Chloride-Bridged Dimers in CH₂Cl₂ Solution
  作者：Jean Huhmann-Vincent、Brian L. Scott、Gregory J. Kubas

  DOI：10.1021/ic980912q

  日期：1999.1.1

  The solvent-coordinated complexes [cis-Re(CO)(4)(PR3)(S)][BArF] (R = Ph, Pr-i, Cy BArF = [B(3,5-(CF3)(2)C6H3)(4)](-)) for S = Et2O. CH(2)Chl(2) and NC5F5 have been prepared from reaction of the neutral methyl precursors, cis-Re-(CO)(4)(PR3)(Me), with either [H(OEt2)(2)][BArF] or [Ph3C][BArF] in the appropriate solvent. A crystal structure of the complex [cis-Re(CO)(4)((PPr3)-Pr-i)(ClCH2Cl)][BArF] shows that the dichloromethane ligand is coordinated through one chlorine, with an Re-Cl distance of 2.554(2) Angstrom. The first example of a structurally characterized pentafluoropyridine complex of rhenium was also determined, [cis-Re(CO)(4)((PPr3)-Pr-i)(NC5F5)][BArF], with an Re-N distance of 2.319(5) Angstrom. Activation of C-CI bonds in the dichloromethane complexes result in the formation of the chloride-bridged dimers, [Cis-Re(CO)(4)(PR3)](2)(mu-Cl)}BArF}, and the X-ray structures of the Ph and Cy derivatives were determined.