Re(Br)(CO)3(2,2'-bipyrimidine) | 934696-72-7

• 英文名称: Re(Br)(CO)3(2,2'-bipyrimidine)
• CAS: 934696-72-7；155761-14-1
• 化学式: C₁₁H₆BrN₄O₃Re
• 分子量: 508.305
• InChiKey: PKDGSBVCONESLZ-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：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  五羰基溴化锰(I) 、 Re(Br)(CO)3(2,2'-bipyrimidine) 以 甲苯 为溶剂， 反应 12.0h， 以89%的产率得到
  参考文献：
  名称：

  双金属 [Mn(CO)3] 和 [Re(CO)3] 配合物的合成、结构研究和氧化还原化学

  摘要：

  锰 ([Mn(CO) 3 ]) 和三羰基铼 ([Re(CO) 3 ]) 配合物代表了主力化合物家族，在各个领域都有应用。在此，探讨了一系列单金属和双金属 [Mn(CO) 3 ] 和 [Re(CO) 3 ] 配合物的配位、结构和电化学性质。特别是，我们合成了一种新型异双金属配合物，该配合物具有由 2,2'-联嘧啶 (bpm) 支撑的 [Mn(CO) 3 ] 和 [Re(CO) 3 ] 单元，并进行了结构表征，并与类似的单体和同质双金属配合物。为了对该系列配合物进行全面的结构分析，我们对七种化合物进行了新的单晶X射线衍射研究：Re(CO) 3 Cl(bpm)、反-[{Re(CO 3 )Cl} 2 (bpm)]、Mn(CO) 3 Br(bpz)（bpz = 2,2′-联吡嗪）、Mn(CO) 3 Br(bpm)、顺式和反式-[{Mn(CO 3 )Br} 2 (bpm)]和syn- [Mn(CO 3

  DOI：

  10.1039/d0dt03666h
• 作为产物：
  描述：

  五羰基溴铼(I) 、 2 2'-联嘧啶 以 甲苯 为溶剂， 反应 22.0h， 生成 Re(Br)(CO)3(2,2'-bipyrimidine)
  参考文献：
  名称：

  双金属 [Mn(CO)3] 和 [Re(CO)3] 配合物的合成、结构研究和氧化还原化学

  摘要：

  锰 ([Mn(CO) 3 ]) 和三羰基铼 ([Re(CO) 3 ]) 配合物代表了主力化合物家族，在各个领域都有应用。在此，探讨了一系列单金属和双金属 [Mn(CO) 3 ] 和 [Re(CO) 3 ] 配合物的配位、结构和电化学性质。特别是，我们合成了一种新型异双金属配合物，该配合物具有由 2,2'-联嘧啶 (bpm) 支撑的 [Mn(CO) 3 ] 和 [Re(CO) 3 ] 单元，并进行了结构表征，并与类似的单体和同质双金属配合物。为了对该系列配合物进行全面的结构分析，我们对七种化合物进行了新的单晶X射线衍射研究：Re(CO) 3 Cl(bpm)、反-[{Re(CO 3 )Cl} 2 (bpm)]、Mn(CO) 3 Br(bpz)（bpz = 2,2′-联吡嗪）、Mn(CO) 3 Br(bpm)、顺式和反式-[{Mn(CO 3 )Br} 2 (bpm)]和syn- [Mn(CO 3

  DOI：

  10.1039/d0dt03666h

文献信息

• Ligand Variations in [ReX(diimine)(CO) ₃ ] Complexes: Effects on Photocatalytic CO ₂ Reduction
  作者：Philipp Kurz、Benjamin Probst、Bernhard Spingler、Roger Alberto

  DOI：10.1002/ejic.200600166

  日期：2006.8

  series of complexes [MX(diimine)(CO)3] (M = Tc, Re) have been prepared, fully characterised and investigated for their ability to act as photocatalysts for the reduction of CO2 to CO. One series consists of complexes with different aromatic diimine ligands while keeping X = Br– constant. The second series describes complexes with diimine = 2,2-bipyridine and variations in the anionic ligand X–. Although

  已经制备了两个系列的复合物 [MX(diimine)(CO)3] (M = Tc, Re)，并对其作为光催化剂将 CO2 还原为 CO 的能力进行了充分表征和研究。一个系列由具有不同的芳族二亚胺配体，同时保持 X = Br– 恒定。第二个系列描述了与二亚胺 = 2,2-联吡啶的配合物以及阴离子配体 X– 的变化。尽管之前已经制备和研究了许多此类配合物，但尚未对其光催化活性进行系统研究。对这些配合物进行了电化学和光谱表征，目的是更好地了解它们各自在光催化 还原中的活性。尽管进行了各种修改，所有显示荧光的化合物都保留了催化活性，包括 [99TcCl(bipy)(CO)3]，而非荧光化合物不会将 转化为 CO。催化活性与光谱或电化学特性（如吸收或发射波长、氧化还原电位）的相关性或 Stern-Volmer 常数对于受激配合物的还原猝灭是困难的。尽管如此，该研究强调了通过配体变化获得具有广泛物理化学性质的
• Influence of Hetero‐Biaryl Ligands on the Photo‐Electrochemical Properties of [Re ^I NCS(N ^∩ N)(CO) ₃ ]‐Type Photosensitizers
  作者：Mathias Mosberger、Benjamin Probst、Bernhard Spingler、Roger Alberto

  DOI：10.1002/ejic.201900652

  日期：2019.8.15

  A complete set of the symmetrical bidiazine (bdz) and asymmetrical pyridyldiazine (pydz) ligands, along with the known 2,2′‐bipyridyl (bpy) ligand, and their respective rhenium(I)‐tricarbonyl‐bromo and ‐thiocyonato complexes are presented. A bathochromic shift is observed with an increasing number of nitrogen atoms, caused by a stabilization of the diimine based LUMO. As expected from the energy gap

  提供了一套完整的对称双二嗪 (bdz) 和不对称吡啶基二嗪 (pydz) 配体，以及已知的 2,2'-联吡啶 (bpy) 配体，以及它们各自的铼 (I)-三羰基-溴和-硫氰化配合物. 由于基于二亚胺的 LUMO 的稳定性，随着氮原子数量的增加，观察到红移。正如能隙定律所预期的那样，这导致沿 bpy-pydz-bdz 线的非辐射衰减常数 (knr) 增加。有趣的是，与其他 pydz 配体（2-（吡啶-2-基）哒嗪（pypdz）和 3,3'-联哒嗪（bpdz））相比，两种哒嗪配体的 knr 增加并不明显。bdz 配体。这导致整体寿命和量子产率更长，
• The case of [(bpm)Re(CO)3Br] and anti-[Br(CO)3Re(μ-bpm)Re(CO)3Br] (bpm: 2,2′-bipyrimidine) towards multi-metallic ReI species and their properties
  作者：Pablo Mella、Roxana Arce、Nancy Pizarro、Andrés Vega

  DOI：10.1016/j.poly.2021.115436

  日期：2021.11
• 1,2-Metallotropic shifts in tricarbonylrhenium(I) complexes of pyridazine (pydz): a dynamic NMR investigation of the effects of cis-chelating ligands
  作者：Edward W. Abel、Peter J. Heard、Keith G. Orrell

  DOI：10.1016/s0020-1693(96)05339-x

  日期：1997.2

  Complexes of general formula fac-[Re(CO)(3)(L-L)(pydz)][BF4] (L-L=neutral bidentate chelate ligand; pydz=pyridazine) were prepared in high yield from fac-[ReBr(CO)(3)(L-L)]. The pyridazine ligand coordinates to the metal moiety in a monodentate fashion, and undergoes a facile intramolecular 1,2-Re-N shift. The kinetics of the 1,2-metallotropic shift were measured by either one-dimensional NMR bandshape analysis or two-dimensional exchange spectroscopy. The free energies of activation, Delta G(not equal) (298 K), were found to be dependent on the nature of the chelate ligand, and were in the range 77-87 kl mol(-1). The origins of the chelate ligand effects are discussed.
• 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.