[Re(MeCN)Br3(PPh3)2] | 1072922-74-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: [Re(MeCN)Br3(PPh3)2]
• CAS: 1072922-74-7；16009-61-3
• 化学式: C₃₈H₃₃Br₃NP₂Re
• 分子量: 991.553
• InChiKey: AKKJEEDYFLCEAK-UHFFFAOYSA-K

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
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• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
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• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  [Re(MeCN)Br3(PPh3)2] 、 双[2-（二-叔丁基膦基)乙基]胺 在 三乙胺 作用下， 以 四氢呋喃 为溶剂， 反应 4.0h， 以81%的产率得到[ReBr₂(PNP)]
  参考文献：
  名称：

  铼钳形配合物还原二氮的卤化物效应

  摘要：

  过渡金属卤化物配合物用作还原 N 2活化直至完全分裂成氮化物配合物的前体。经常观察到卤化物对氧化还原性质和产率的不同影响，但尚未得到很好的理解。在这里，还原性 N 2与铼 (III) 配合物 [ReX 2 (PNP)] (PNP = N(CH 2 CH 2 P t Bu 2 ) 2和 X = Cl, Br, I)的电化学和计算检查被呈现。如先前关于氯化物前体的报道（J. Am. Chem. Soc. 2018 , 140, 7922)，较重的卤化物在（电）化学还原时以良好的产率产生铼 (V) 氮化物，但沿卤化物系列具有显着的阳极偏移电解电位。双核末端 N 2桥接复合物 [{ReX(PNP)} 2 (μ-N 2 )] 在所有情况下都被确定为关键中间体。然而，虽然氯化物络合物仅通过 2 电子还原和 Re III /Re I比例化形成，但碘化物系统还通过替代的 Re II /Re II 二聚机制

  DOI：

  10.1021/acs.inorgchem.2c00973
• 作为产物：
  描述：

  oxotribromobis(triphenylphosphine)rhenium(V) 、 N,N-Bis(trimethylsilyl)aminodiphenylphosphan 、 三苯基膦 、 乙腈 以 乙腈 为溶剂， 以52%的产率得到[ReBr2(MeCN)(PPh3)2(N=C(CH3)P(O)Ph2]
  参考文献：
  名称：

  钛，钨和钌的二芳基磷腈和二芳基膦酰肼配合物以及of的磷酰酮亚胺基配合物的制备和表征。

  摘要：

  配体Ph2PN（SiMe3）2（L1）与WCl6反应得到低聚磷腈配合物[WCl4（NPPh2）] n，1，随后与PMe2Ph或NBu4Cl反应得到[WCl4（NPPh2）（PMe2Ph）]（2）或[ WCl5（NPPh2）] [NBu4]（3）。在[WCl5（NPPh2）] [NBu4]上的DF计算表明，W = N双键（1.756 A），PN键距离为1.701 A，这与P原子的几何形状相结合，表明没有PN多重键。L1与MeCN中的[ReOX3（PPh3）2]反应（X = Cl或Br）得到[ReX2（NC（CH3）P（O）Ph2）（MeCN）（PPh3）]（X = Cl，4，X = Br，5），其中含有新的磷酸基酮亚胺基配体。它通过几乎线性的Re-NC排列（Re-NC角度= 176.6度，当X = Cl时）绑定到the中心，并且Re和N之间存在多重键合（当X时Re-N = 1.809（7）A

  DOI：

  10.1039/b417068g

文献信息

• Photoelectrochemical Conversion of Dinitrogen to Benzonitrile: Selectivity Control by Electrophile‐ versus Proton‐Coupled Electron Transfer
  作者：Maximilian Fritz、Severine Rupp、Ciara I. Kiene、Sesha Kisan、Joshua Telser、Christian Würtele、Vera Krewald、Sven Schneider

  DOI：10.1002/anie.202205922

  日期：2022.8.26

  is mediated by a Re pincer complex. The resulting ReV nitride undergoes electrochemical N-atom transfer in the presence of benzoyl bromide and acid at mild potentials. The high selectivity with respect to nitrile formation is attributed to the unfavorable thermochemistry of proton-coupled electron transfer (PCET) to the nitride.

  展示了一种在简单的两步循环内将N 2转化为苯甲腈的新策略。N 2的光电化学还原分裂由 Re pincer 复合物介导。生成的 Re V氮化物在苯甲酰溴和酸的存在下在温和电位下发生电化学 N 原子转移。对腈形成的高选择性归因于质子耦合电子转移 (PCET) 对氮化物的不利热化学。
• New complexes of rhenium-(<scp>V</scp>) or -(<scp>III</scp>) with various diphosphines or bis(diphenylphosphino)methane monoxide: crystal structure of mer-[ReCl₃(dppm-PP′)(dppom-P)][dppm = Ph₂PCH₂PPh₂, dppom = Ph₂PCH₂P(O)Ph₂]
  作者：Xavier L. R. Fontaine、Edmund H. Fowles、Timothy P. Layzell、Bernard L. Shaw、Mark Thornton-Pett

  DOI：10.1039/dt9910001519

  日期：——

  Treatment of [ReOCl3(AsPh3)2] or [ReOBr3(AsPh3)2] with the diphosphines, Ph2PCH2PPh2 (dppm), Ph2PC(= CH2)PPh2 (vdpp), cis-Ph2PCH = CHPPh2 (dppen), or Ph2PCHMePPh2 (1,1'-dppe) gave complexes of the type [ReOX3(L-L)] (L-L = chelating diphosphine, X = Cl or Br), in high yield. Treatment of [ReOCl3(AsPh3)2] with an excess of dppm at 20-degrees-C caused some reduction to give a mixture of two rhenium(III) complexes [ReCl3(dppm-PP')(dppom-P)] 2a [dppom = Ph2PCH2P(= O)Ph2] and [ReCl3(dppm-PP')(dppm-P)] 3a, which was difficult to separate. Treatment of [ReOCl3(AsPh3)2] with 2 mol of dppm in hot benzene gave pure 2a, whilst treatment of [ReCl3(NCMe)(PPh3)2] with 4-5 mol equivalents of dppm in hot benzene gave 3a in excellent yield. The tribromide analogue [ReBr3(dppm-PP')(dppom-P)] was prepared by heating [ReOBr3(dppm-PP')] with dppm. On treating [ReBr3(NCMe)(PPh3)2] with dppm, [ReBr3(dppm-PP')(dppm-P)] was formed but this was contaminated with the isomeric salt [ReBr2(dppm-PP')2]Br from which it could not be separated; however the NMR parameters for both components were assigned. The pure salt [ReBr2(dppm-PP')2]BPh4 was prepared from the mixture. In their H-1 NMR spectra, these rhenium(III) complexes show large paramagnetic shifts for the methylene protons of the chelated dppm and for some of the ortho-protons. Some of these resonances were assigned using two-dimensional correlation spectroscopy and nuclear Overhauser effect experiments. Crystals of complex 2a are monoclinic, space group P2(1)/n, with a = 1147.7(4), b = 2315.5(6), c = 2069.7(6) pm, beta = 91.76(3)-degrees and Z = 4; final R factor 0.0465 for 6150 observed reflections. The structure shows octahedral co-ordination with a mer arrangement of chlorines, a chelated dppm and a monodentate dppm monoxide, with the P = O group unco-ordinated.
• Tisato, Francesco; Refosco, Fiorenzo; Bolzati, Cristina, Journal of the Chemical Society, Dalton Transactions, 1997, # 8, p. 1421 - 1427
  作者：Tisato, Francesco、Refosco, Fiorenzo、Bolzati, Cristina、Cagnolini, Aldo、Gatto, Stefano、Bandoli, Giuliano

  DOI：——

  日期：——
• Synthesis, characterization and molecular structure of Re(III) complexes containing 2-benzoylpyridine
  作者：B. Machura、J. Mroziński、J. Kusz

  DOI：10.1016/j.inoche.2009.11.019

  日期：2010.2

  The paper presents a combined experimental and computational study of Re(III) complexes containing 2-benzoylpyridine (bopy). Two novel complexes [ReX(3)(bopy)(PPh(3))] (X = Cl, Br) have been obtained in the reactions of [ReX(3)(MeCN)(PPh(3))(2)] with 2-benzoylpyridine in dichloromethane and have been studied by IR, UV-Vis spectroscopy and X-ray crystallography. The electronic structure of [ReCl(3)(bopy)(PPh(3))] has been calculated with the density functional theory (DFT) method. The spin-allowed electronic transitions of [ReCl(3)(bopy)(PPh(3))] have been calculated with the time-dependent DFT method and the UV-Vis spectrum has been discussed on this basis. (C) 2009 Elsevier B.V. All rights reserved.
• Seven-coordinate rhenium(III) complexes of 1-(2-pyridylazo)-2-naphtholate: X-ray studies, spectroscopic characterization and DFT calculations
  作者：B. Machura、J. Mroziński、R. Kruszynski、J. Kusz

  DOI：10.1016/j.poly.2008.06.012

  日期：2008.9

  The reactions of [ReX3(MeCN)(PPh3)(2)] (X = Cl or Br) with 1-(2-pyridylazo)-2- naphthol (HPAN) have been examined and the [ReBr(PAN)(2)] center dot 2CHCl(3) (1) and [ReCl(PAN)(2)] (2) complexes have been obtained. The both complexes have been structurally and spectroscopically characterized, and compound I has been additionally studied by magnetic measurements. The magnetic behavior is characteristic of mononuclear seven-coordinated Re(III) complex with d(4) IOW-spin configuration, which gives diamagnetic ground state. The electronic structure of [ReBr(PAN)21 has been calculated with the density functional theory (DFT) method. The time-dependent DFT calculations have been employed to calculate the electronic spectrum of [ReBr(PAN)(2)], and the UV-Vis spectra of the [ReX(PAN)(2)] compounds have been discussed on this basis. (c) 2008 Elsevier Ltd. All rights reserved.