(2,2'-bipyrimidine)Re(CO)3Cl | 104910-06-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二嗪类
• 英文名称: (2,2'-bipyrimidine)Re(CO)3Cl
• 英文别名: [Re(CO)3Cl(2,2'-bipyrimidine)]；[Re(2,2'-bipyrimidine)(CO)3Cl]；carbon monoxide;chlororhenium;2-pyrimidin-2-ylpyrimidine
• CAS: 104910-06-7
• 化学式: C₁₁H₆ClN₄O₃Re
• 分子量: 463.854
• InChiKey: MBKNZPXSIZZHGC-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  1.51
• 重原子数：
  20
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  54.6
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  (bicyclo[2.2.1]hepta-2,5-diene)tetracarbonylmolybdenum(0) 、 (2,2'-bipyrimidine)Re(CO)3Cl 以 四氢呋喃 为溶剂， 以69%的产率得到{(tetracarbonyl)molybdenum(μ-2,2'-bipyrimidine)(tricarbonyl)rhenium chloride}
  参考文献：
  名称：

  Matheis, W.; Kaim, W., Zeitschrift fur Anorganische und Allgemeine Chemie

  摘要：

  DOI：
• 作为产物：
  描述：

  五羰基氯铼(I) 、 2 2'-联嘧啶 以 甲苯 为溶剂， 生成 (2,2'-bipyrimidine)Re(CO)3Cl
  参考文献：
  名称：

  Re I的配体桥联同核和杂核羰基聚吡啶基配合物：合成，电子光谱，氧化还原和发光行为

  摘要：

  报告了Re I的一系列单和配体桥联的双核羰基聚吡啶基络合物的电子吸收数据，氧化还原电势和光物理性质：Re {[ReCl（CO）3 } n L b ]和[（OC）3 ClRe（L b）M（bipy）2 ] 2+ [桥联配体（L b）= 2,3-双（2'-吡啶基）吡嗪（dpp）或2,3-双（2'-吡啶基）喹喔啉（ dpq）; bipy = 2,2'-联吡啶; M = Ru II或Os II ; ñ= 1或2]。对于所有检查的双核配合物，电子吸收和电化学数据表明在双核作用下配体π*轨道的广泛稳定。这些也是重的强耦合配体桥联的二聚配合的第一例我的是在室温下在溶液表现出致发光（电荷转移型）。关于Re和Ru的异双核配合物的发射最大值和寿命的数据证实了较早的迹象，即发射状态基本上位于Ru→L b电荷转移上。

  DOI：

  10.1039/dt9900001657

文献信息

• Bipyrimidine-bridged rhenium(I)/rhenium(I) and ruthenium(II)/rhenium(I) complexes. Synthesis, electronic absorption and emission spectra
  作者：A. Vogler、J. Kisslinger

  DOI：10.1016/s0020-1693(00)84413-8

  日期：1986.5

  The binuclear complexes [Cl(OC)3ReI(bipym)ReI(CO)3Cl] (bipym=2,2′-bipyrimidine), [(bipy)2RuII(bipym)ReI(CO)3Cl](PF6)2 (bipy=2,2′-bipyridine) and their mononuclear component [Re(bipym)(CO)3Cl] were prepared. The electronic absorption spectra of these complexes display low-energy Re(I) →π*(bipym) and Ru(II)→π*(bipym) charge transfer (CT) bands. While [Re(bipym)(CO)3Cl] shows a strong emission from its

  双核络合物[Cl（OC）3 Re I（bipym）Re I（CO）3 Cl]（bipym = 2,2'-bipyrimidine），[（bipy）2 Ru II（bipym）Re I（CO）3 Cl制备]（PF 6）2（bipy = 2,2'-联吡啶）及其单核成分[Re（bipym）（CO）3 Cl]。这些配合物的电子吸收光谱显示出低能量的Re（I）→π*（bipym）和Ru（II）→π*（bipym）电荷转移（CT）带。尽管[Re（bipym）（CO）3 Cl]从其最低的CT状态显示出强发射，但二聚体[Cl（OC）3 Re（bipym）Re（CO）3Cl]不发光。阳离子[（bipy）2 Ru（bipym）Re（CO）3 Cl] 2+从最低能量的Ru→bipym CT状态发出。双核络合物的发射行为用分子内激发态电子或能量转移来描述。
• Syntheses and Crystal Structures of Dinuclear Complexes Containing d-Block and f-Block Luminophores. Sensitization of NIR Luminescence from Yb(III), Nd(III), and Er(III) Centers by Energy Transfer from Re(I)− and Pt(II)−Bipyrimidine Metal Centers
  作者：Nail M. Shavaleev、Gianluca Accorsi、Dalia Virgili、Zöe R. Bell、Theodore Lazarides、Giuseppe Calogero、Nicola Armaroli、Michael D. Ward

  DOI：10.1021/ic048875s

  日期：2005.1.1

  CH(2)Cl(2) solution, partial dissociation of the dinuclear complexes into the mononuclear units occurs, with the result that some (3)MLCT luminescence is observed from mononuclear [Re(bpym)(CO)(3)Cl] or [Pt(bpym)(CC-C(6)H(4)CF(3))(2)] present in the equilibrium mixture. Solution UV-vis and luminescence titrations, carried out by the addition of portions of Ln(fod)(3)(H(2)O)(2) or Ln(hfac)(3)(H(2)O)(2)

  单核络合物[Re（bpym）（CO）（3）Cl]和[Pt（bpym）（CC-C（6）H（4）CF（3））（2）]（bpym = 2,2'-联嘧啶）（其中一个双嘧啶位点是空位）已用作制备异双核df复合物，其中镧系元素三（1,3-二酮）单元连接至第二个双嘧啶位点，以评估d嵌段发色团充当触角，从邻近的镧系元素（III）中心引起敏化的近红外（NIR）发光。如此制备的两组络合物为[Re（CO）（3）Cl（mu-bpym）Ln（fod）（3）]（缩写为Re-Ln；其中Ln = Yb，Nd，Er）和[[F （3）CC（6）H（4）-CC）（2）Pt（μ-bpym）Ln（hfac）（3）]（缩写为Pt-Ln；其中Ln ＝ Nd，Gd）。这两个系列的成员都具有结构特征；跨联嘧啶桥的金属-金属间距约为6。每种情况下为3A。在这些配合物中，单核[Re（bpym）（CO）（3）Cl]和[Pt（bpym）（CC-C（6）H）
• A simple, general synthesis of mixed d–f complexes containing both {Re(CO)₃Cl(diimine)} and lanthanide-tris(β-diketonate) luminophores linked by bis-diimine bridging ligands
  作者：Nail M. Shavaleev、Zöe R. Bell、Michael D. Ward

  DOI：10.1039/b207832e

  日期：——

  Reaction of the mononuclear ‘complex ligands’ [Re(CO)3Cl(L)] [L = 2,2′-bipyrimidine (bpym) or 2,3-bis(2-pyridyl)pyrazine (bppz)] with a Ln(β-diketonate)3 unit affords the heterodinuclear complexes [Re(CO)3Cl(μ-bpym)Ln(fod)3] and [Re(CO)3Cl(μ-bppz)Ln(tta)3]; one member of each series has been structurally characterised.

  单核络合物配体[Re(CO)3Cl(L)][L = 2,2â²-联嘧啶（bpym）或 2、3-双(2-吡啶基)吡嗪 (bppz)]与 Ln(δ-二酮酸)3单元的异核配合物产生了[Re(CO)3Cl(δ-bpym)Ln(fod)3]和[Re(CO)3Cl(δ-bppz)Ln(ta)3]；每个系列中都有一个成员已经过结构表征。
• Sahai, Ram; Rillema, D. Paul; Shaver, Randy, Inorganic Chemistry, 1989, vol. 28, # 6, p. 1022 - 1028
  作者：Sahai, Ram、Rillema, D. Paul、Shaver, Randy、Van Wallendael, Shawn、Jackman, Donald C.、Boldaji, Massoud

  DOI：——

  日期：——
• Photochemistry and Emission of the Dinuclear Complexes (CO)5MnRe(CO)3(L) (L = 2,2'-Bipyrimidine, 2,3-Bis(2-pyridyl)pyrazine) and Bridged Trinuclear Complexes (CO)5MnRe(CO)3(L)Re(Br)(CO)3 and (CO)5MnRe(CO)3(BPYM)W(CO)4: Effect of the Remote Metal Center on the Photodissociation of the Mn-Re Bond
  作者：J. W. M. van Outersterp、D. J. Stufkens、A. Vlcek

  DOI：10.1021/ic00125a016

  日期：1995.10

  Photochemical and emission properties of the dinuclear (CO)(5)MnRe(CO)(3)(L) and trinuclear (CO)(5)MnRe(CO)(3)(L)Re(Br)(CO)(3) and (CO)(5)MnRe(CO)(3)(BPYM)W(CO)(4) complexes (L = 2,2'-bipyrimidine (BPYM), 2,3-bis(2-pyridyl)pyrazine (DPP)) are described. All these compounds undergo photochemical homolysis of the Mn-Re bond upon excitation into their MLCT absorption band(s) in the visible spectral region. Mn(Cl)(CO)(5) and Re(Cl)(CO)(3)(L) or Re(Cl)(CO)(3)(L)Re(Br)(CO)(3) are formed in chlorinated solvents (CH2Cl2, CCl4) from the former two types of complexes, respectively. In THF, photolysis produces Mn-2(CO)(10), together with [Re(CO)(3)(L)](.), [Re(CO)(3)(L)Re(Br)(CO)(3)](.), or [Re(CO)(3)(BPYM)W(CO)(4)](.) radicals, respectively, which presumably contain also a coordinated THF molecule. Photoreactions of the dinuclear complexes occur with high quantum yields (0.36 for BPYM and 0.54 for DPP), which are independent of the temperature and of the excitation wavelength. The attachment of the Re(Br)(CO)(3) group to the potentially bridging ligand L in (CO)(5)MnRe(CO)(3)(L) to form the L-bridged trinuclear species strongly influences the excited state dynamics involved in the photochemistry. Thus, the photochemical quantum yields of the trinuclear complexes are both temperature and excitation wavelength dependent. The apparent activation energy, together with the overall quantum yield, decreases upon changing the excitation from the high- to the low-energy MLCT absorption band. The Mn-Re bond homolysis is about 6 times more efficient for bridging DPP than for bridging BPYM. The dinuclear complexes exhibit, in a 2-MeTHF glass at 80 K, an emission from thermally unequilibrated states, whereas double emission, extending into the near-IR spectral region, was observed for (CO)(2)MnRe(CO)(3)(DPP)Re(Br)(CO)(3). Its BPYM analogue is nonemissive. To account for this complex photobehavior, an excited state diagram and a qualitative dynamics model are proposed. The reaction is assumed to occur from a 3 sigma pi* state that is nonradiatively populated from the higher MLCT state(s). The main effects of the attachment of the Re(Br)(CO)(3) group, which is responsible for the changed photochemical behavior, are the profound stabilization of the pi* LUMO of the bridging ligand L and the introduction of another MLCT excited state into the trinuclear molecule.