[Re(4,4'-Me2-2,2'-bipyridine)(CO)3(P(OEt)3)](PF6) | 186969-34-6

• 英文名称: [Re(4,4'-Me2-2,2'-bipyridine)(CO)3(P(OEt)3)](PF6)
• 英文别名: [(4,4'-dimethyl-2,2'-bipyridine)Re(CO)3(P(OEt)3)](PF6)
• CAS: 186969-34-6
• 化学式: C₂₁H₂₇N₂O₆PRe*F₆P
• 分子量: 765.6
• InChiKey: LJTSNTIIRXUDKI-UHFFFAOYSA-N

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：

  [Re(4,4'-Me2-2,2'-bipyridine)(CO)3(P(OEt)3)](PF6) 以 N,N-二甲基甲酰胺 为溶剂， 生成 [Re(4,4'-Me2-2,2'-bipyridine)(CO)3(P(OEt)3)]
  参考文献：
  名称：

  Key Process of the Photocatalytic Reduction of CO₂ Using [Re(4,4‘-X₂-bipyridine)(CO)₃PR₃]⁺ (X = CH₃, H, CF₃; PR₃ = Phosphorus Ligands):  Dark Reaction of the One-Electron-Reduced Complexes with CO₂

  摘要：

  Reduction of CO2 to CO was efficiently photocatalyzed by [Re(4,4'-X(2)bpy)(CO)(3)PR3](+) (X = H, Me; PR3 = P(OEt)(3), P(O-i-Pr)(3)) in quantum yields of 0.16-0.20. Complexes with CF3 as X or trialkylphosphine as PR3 have much lower photocatalytic ability. One-electron-reduced species of the complexes, which were produced by the photoinduced electron-transfer reaction with triethanolamine, reacted with CO2 in the dark with rate constants of 3.5 x 10(-4)-1.9 x 10(-2) M-1 s(-1). The faster the rate of this process, the higher the quantum yield of CO formation. The calculated amount of CO formation, based on the assumption that the process gives CO quantitatively, was similar to the actually observed amount under various conditions. This is consistent with the thermal process being one of the rate-limiting steps in the photocatalyzed reduction of CO2 by the rhenium complexes.

  DOI：

  10.1021/om970608p
• 作为产物：
  描述：

  [Re(4,4'-dimethyl-2,2'-bipyridine)(CO)₃(CH₃CN)](PF₆) 、 亚磷酸三乙酯 以 四氢呋喃 为溶剂， 以89%的产率得到[Re(4,4'-Me2-2,2'-bipyridine)(CO)3(P(OEt)3)](PF6)
  参考文献：
  名称：

  双核铼（我）配合物的光催化还原的CO 2 †

  摘要：

  双核rh（I）与1,2-双（4,4'-甲基-[[2,2']联吡啶基）-乙烷和1,2-双（4,4'-甲基-[2,2']的配合物作为桥联配体的双吡啶基）-十二烷及其单核类似物已经合成并通过其光谱学和电化学性质进行了表征。烷基接头不影响第一还原电势和发光性质以及TEOA的发射态的还原猝灭。通过对单金属配合物和双金属配合物的光催化CO 2还原的详细比较，发现了对活性的巨大有益作用，这取决于中心的接近程度。在高稀释度下，CO 2中的整体动力学单核络合物的光还原显然是单金属的。如果根据OER（一种电子还原物种）的寿命来调节中心的接近度，则光催化活性将大大提高，显示出清晰的双金属机理。在双核rh络合物中，可以实现简便的自由配位位点生成和有效的两个电子转移的双核相互作用。

  DOI：

  10.1039/c2dt30273j
• 作为试剂：
  描述：

  二氧化碳 在 [Re(4,4'-Me2-2,2'-bipyridine)(CO)3(P(OEt)3)](PF6) 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 生成 一氧化碳
  参考文献：
  名称：

  Key Process of the Photocatalytic Reduction of CO₂ Using [Re(4,4‘-X₂-bipyridine)(CO)₃PR₃]⁺ (X = CH₃, H, CF₃; PR₃ = Phosphorus Ligands):  Dark Reaction of the One-Electron-Reduced Complexes with CO₂

  摘要：

  Reduction of CO2 to CO was efficiently photocatalyzed by [Re(4,4'-X(2)bpy)(CO)(3)PR3](+) (X = H, Me; PR3 = P(OEt)(3), P(O-i-Pr)(3)) in quantum yields of 0.16-0.20. Complexes with CF3 as X or trialkylphosphine as PR3 have much lower photocatalytic ability. One-electron-reduced species of the complexes, which were produced by the photoinduced electron-transfer reaction with triethanolamine, reacted with CO2 in the dark with rate constants of 3.5 x 10(-4)-1.9 x 10(-2) M-1 s(-1). The faster the rate of this process, the higher the quantum yield of CO formation. The calculated amount of CO formation, based on the assumption that the process gives CO quantitatively, was similar to the actually observed amount under various conditions. This is consistent with the thermal process being one of the rate-limiting steps in the photocatalyzed reduction of CO2 by the rhenium complexes.

  DOI：

  10.1021/om970608p

文献信息

• New Synthetic Routes to Biscarbonylbipyridinerhenium(I) Complexes <i>cis,trans</i>-[Re(X₂bpy)(CO)₂(PR₃)(Y)]<i>ⁿ</i>⁺ (X₂bpy = 4,4‘-X₂-2,2‘-bipyridine) via Photochemical Ligand Substitution Reactions, and Their Photophysical and Electrochemical Properties
  作者：Kazuhide Koike、Junji Tanabe、Shigeki Toyama、Hideaki Tsubaki、Kazuhiko Sakamoto、Jeremy R. Westwell、Frank P. A. Johnson、Hisao Hori、Hideki Saitoh、Osamu Ishitani

  DOI：10.1021/ic991190l

  日期：2000.6.1

  pyridine, PR'3), were synthesized in good yields via photochemical ligand substitution reactions. The structure of cis,trans-[Re(Me2bpy)(CO)2[P(OEt)3](PPh3)](PF6) was determined by X-ray analysis. Crystal data: C38H42N2O5F6P3Re, monoclinic, P2(1/a), a = 11.592(1) A, b = 30.953(4) A, c = 11.799(2) A, V = 4221.6(1) A3, Z = 4, 7813 reflections, R = 0.066. The biscarbonyl complexes with two phosphorus ligands

  fac- [Re（X2bpy）（CO）3（PR3）] +的光化学配体取代（X2bpy = 4,4'-X2-2,2'-联吡啶; X = Me，H，CF3; R = OEt，Ph ）与乙腈定量给出了新型的双羰基配合物，顺式，反[Re（X2bpy）（CO）2（PR3）（MeCN）] +，与四种不同类型的配体配合。同样，其他双羰基hen配合物，顺式，反式-[Re（X2bpy）（CO）2（PR3）（Y）] n +（n = 0，Y = Cl-； n = 1，Y =吡啶，PR'3），通过光化学配体取代反应以高收率合成了这些化合物。通过X射线分析确定了顺式，反式-[Re（Me2bpy）（CO）2 [P（OEt）3]（PPh3）]（PF6）的结构。晶体数据：C38H42N2O5F6P3Re，单斜晶系，P2（1 / a），a = 11.592（1）A，b = 30.953（4）A，c = 11.799（2）A，V
• Non-photochemical synthesis of Re(diimine)(CO)2(L)Cl (L = phosphine or phosphite) compounds
  作者：Daniel A. Kurtz、Badrinath Dhakal、Elizabeth S. Donovan、Gary S. Nichol、Greg A.N. Felton

  DOI：10.1016/j.inoche.2015.07.001

  日期：2015.9

  products of analogous PLS pathways. The substitution of a carbonyl group by a phosphine/phosphite ligands shifts absorption further into the visible region without diminishing molar absorptivity. The synthesis presented provides a general facile ligand substitution pathway for related light-sensitive neutral rhenium/manganese carbonyl halide compounds.

  摘要 报道了一系列 Re(二亚胺)(CO)2(L)Cl（其中 L = P(OEt)3，PMe3）类型的化合物的合成和表征。非光化学配体取代 (non-PLS) 利用磷配体的转稳定作用来促进羰基取代。非 PLS 途径导致单一异构体产品的高产率 (> 60%)，与类似 PLS 途径的低产率、混合异构体产品相比具有优势。羰基被膦/亚磷酸酯配体取代，将吸收进一步转移到可见光区域，而不会降低摩尔吸收率。所提出的合成为相关的光敏中性铼/锰羰基卤化物化合物提供了一种通用的简便配体取代途径。