[Re(Cl)(CO)3(4,4'-dimethyl-2,2'-bipyridine)] | 99666-78-1

• 英文名称: [Re(Cl)(CO)3(4,4'-dimethyl-2,2'-bipyridine)]
• 英文别名: Re(4,4'-dimethyl-2,2'-bipyridine)(CO)3Cl
• CAS: 99666-78-1
• 化学式: C₁₅H₁₂ClN₂O₃Re
• 分子量: 489.932
• InChiKey: OCDGGAVRJFBKFU-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：
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• 氢受体数：
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反应信息

• 作为反应物：
  描述：

  [Re(Cl)(CO)3(4,4'-dimethyl-2,2'-bipyridine)] 、 甲基氯化镁 以 四氢呋喃 为溶剂， 生成 fac-[Re(Me)(CO)3(4,4'-dimethyl-2,2'-bipyridine)]
  参考文献：
  名称：

  [Re（R）（CO）3（4,4'-dimethyl-2,2'-bipyridine）]中光化学Re-Me和Re-Et键均解的不同机理。时间分辨的红外光谱研究，范围从皮秒到微秒§

  摘要：

  通过红外光谱在ν（CO）光谱范围内研究了[Re（R）（CO）3（dmb）]（R =甲基（Me），乙基（Et））的两种金属-烷基络合物的光化学，在从皮秒到微秒的异常宽泛的时间范围内进行时间分辨。MeCN中[Re（Et）（CO）3（dmb）]的光激发在头两个皮秒内产生自由基[Re（MeCN）（CO）3（dmb）] •和Et •以及激发态，转换为相同自由基的速度较慢（约90 ps）。反应性激发态被确定为3 MLCT（金属到配体的电荷转移），具有3 SBLCT（σ键到配体的电荷转移）特征的混合物。英寸2 Cl 2溶液，该激发态与溶剂分子反应生成自由基阴离子[Re（Cl）（CO）3（dmb）] • -约130 ps动力学。随后发生一系列较慢的反应，形成[Re（CH 2 Cl 2）（CO）3（dmb）] •并最终形成[Re（Cl）（CO）3（dmb）]。[Re（Me）（CO）3（dmb）]的光化学机理

  DOI：

  10.1021/om0508886
• 作为产物：
  描述：

  [Re(CO)4(4,4'-dimethyl-2,2'-bipyridine)]Cl 以 N,N-二甲基甲酰胺-d7 为溶剂， 以84%的产率得到[Re(Cl)(CO)3(4,4'-dimethyl-2,2'-bipyridine)]
  参考文献：
  名称：

  Synthesis and properties of fac-Re(dmbpy)(CO)3CHO (dmbpy = 4,4′-dimethyl-2,2′-bipyridine), a possible intermediate in reductions of CO2 catalyzed by fac-Re(dmbpy)(CO)3Cl

  摘要：

  Synthesis of fac-Re(dmbpy)(CO)3CHO 2 and its reactions with CO2 in DMF and DMSO have been conducted; 2 transfers hydride to CO2 to give Re(dmbpy)(CO)4+ OCHO− 5 which is rapidly transformed to fac-Re(dmbpy)(CO)3- (OCHO) 3 in DMF, thus supporting the viability of 2 in photocatalytic reactions of fac-Re(dmbpy)(CO)3Cl with CO2.

  DOI：

  10.1039/b106270k

文献信息

• Photophysics and ultrafast processes in rhenium(<scp>i</scp>) diimine dicarbonyls
  作者：Hala Atallah、Chelsea M. Taliaferro、Kaylee A. Wells、Felix N. Castellano

  DOI：10.1039/d0dt01765e

  日期：——

  In this work, a series of nine Re(I) diimine dicarbonyl complexes of the general molecular formula cis-[Re(N^N)2(CO)2]+ (N^N are various 2,2′-bipyridine (bpy) or 1,10-phenanthroline (phen) derivatives) were prepared and spectroscopically investigated to systematically evaluate the photophysical consequences of various substituents resident on the diimine ligands. These panchromatic absorbing chromophores

  在这项工作中，一系列九种通式为顺式-[Re（N ^ N）2（CO）2 ] +的Re（I）二亚胺二羰基配合物（N ^ N是各种2,2'-联吡啶（bpy）或1,10-菲咯啉（phen）衍生物）并进行光谱研究以系统地评估驻留在二亚胺配体上的各种取代基的光物理结果。这些全色吸收发色团经过结构表征，评估了它们的电化学和光谱电化学性质，并使用了静态和动态电子吸收，光致发光（PL）和红外光谱从超快到超纳秒的时间范围进行了研究。电子结构计算进一步支持了超快时间分辨红外（TRIR）分析，该计算表征了两个C内的变化金属-配体电荷转移（MLCT）激发态形成时的O振动模式。这一系列二羰基分子的MLCT激发态衰变似乎与能隙定律行为完全一致，其中非辐射衰变速率常数随激发态-基态能量分离的降低呈对数增加，除非预期的取代基是苯基或叔叔丁基。
• Mabrouk, Patricia A.; Wrighton, Mark S., Inorganic Chemistry, 1986, vol. 25, # 4, p. 526 - 531
  作者：Mabrouk, Patricia A.、Wrighton, Mark S.

  DOI：——

  日期：——
• Involvement of a Binuclear Species with the Re−C(O)O−Re Moiety in CO₂ Reduction Catalyzed by Tricarbonyl Rhenium(I) Complexes with Diimine Ligands:  Strikingly Slow Formation of the Re−Re and Re−C(O)O−Re Species from Re(dmb)(CO)₃S (dmb = 4,4‘-Dimethyl-2,2‘-bipyridine, S = Solvent)
  作者：Yukiko Hayashi、Shouichi Kita、Bruce S. Brunschwig、Etsuko Fujita

  DOI：10.1021/ja035960a

  日期：2003.10.1

  Excited-state properties of fac-[Re(dmb)(CO)(3)(CH3CN)]PF6, [Re(dmb)(CO)(3)](2) (where dmb = 4,4'-dimethyl-2,2'-bipyridine), and other tricarbonyl rhenium(l) complexes were investigated by transient FTIR and UV-vis spectroscopy in CH3CN or THF. The one-electron reduced monomer, Re(dmb)(CO)(3)S (S = CH3CN or THF), can be prepared either by reductive quenching of the excited states of fac-[Re(dmb)(CO)(3)(CH3CN)]PF6 or by homolysis of [Re(dmb)(CO)(3)](2). In the reduced monomer's ground state, the odd electron resides on the dmb ligand rather than on the metal center. Re(dmb)(CO)(3)S dimerizes slowly in THF, k(d) = 40 +/- 5 M-1 s(-1). This rate constant is much smaller than those of other organometallic radicals which are typically 10(9) M-1 s(-1). The slower rate suggests that the equilibrium between the ligand-centered and metal-centered radicals is very unfavorable (K approximate to 10(-4)). The reaction of Re(dmb)(CO)(3)S with CO2 is slow and competes with the dimerization. Photolysis of [Re(dmb)(CO)(3)](2) in the presence of CO2 produces CO with a 25-50% yield based on [Re]. A CO2 bridged dimer, (CO)(3)(dmb)Re-CO(O)-Re(dmb)(CO)(3) is identified as an intermediate. Both [Re(dmb)(CO)(3)](2)(OCO2) and Re(dmb)(CO)(3)(OC(O)OH) are detected as oxidation products; however, the previously reported formato-rhenium species is not detected.
• Combined steric and electronic effects of positional substitution on dimethyl-bipyridine rhenium(I)tricarbonyl electrocatalysts for the reduction of CO 2
  作者：Steven A. Chabolla、Edward A. Dellamary、Charles W. Machan、F. Akif Tezcan、Clifford P. Kubiak

  DOI：10.1016/j.ica.2014.07.007

  日期：2014.10

  The use of CO2 as a chemical feedstock has been the focus of much research in recent years due to the promise for carbon neutral fuel storage in chemical bonds. Specifically, electrocatalysts of the type Re(bpy)(CO)(3)Cl (bpy = 2,2'-bipyridine and analogues thereof) have been studied for their ability to reduce CO2 to CO. These catalysts are among the most active, selective, and robust homogeneous catalysts for CO2 reduction in the literature. Previous studies have involved understanding the mechanism for catalysis and the inductive effect of bipyridine functional groups on catalysis. In the study reported herein, we have assessed the CO2 reduction capabilities of a series of Re(n,n'-dimethyl-bpy)(CO)(3)Cl (n = 3 and 5) catalysts with a bpy modified at the 3 and 5 positions with methyl substituents. While the 5,5'-positional substituents have the effect of increasing catalytic activity (i(cat)/i(p) = 29.6) over the unsubstituted catalyst (i(cat)/i(p) = 20.3); steric hindrance in the 3,3'-substituted bpy has the effect of decreasing catalytic activity (i(cat)/i(p) = 17.0). This decreased catalytic current response can be explained by steric hindrance in the 3,3'-substituted catalyst disfavoring optimal charge transfer in the catalytic cycle. (C) 2014 Elsevier B. V. All rights reserved.