[benzoylhydrazido(3-)-ON']dibromobis(triphenylphosphine)rhenium(V) | 33749-44-9

• 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: [benzoylhydrazido(3-)-ON']dibromobis(triphenylphosphine)rhenium(V)
• 英文别名: [Re(=N-NC(Ph)O-)(PPh3)2Br2]；[ReBr2(η2-N2COPh-N',O)(PPh3)2]
• CAS: 33749-44-9
• 化学式: C₄₃H₃₅Br₂N₂OP₂Re
• 分子量: 1003.73
• InChiKey: YFTJZWJOWPALQS-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 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：

  4-甲基吡啶 、 [benzoylhydrazido(3-)-ON']dibromobis(triphenylphosphine)rhenium(V) 以 乙醇 、 苯 为溶剂， 以75%的产率得到bromotetrakis(dimethylphenylphosphine)(dinitrogen)rhenium(I)
  参考文献：
  名称：

  连接二氮形成碳氮键的反应

  摘要：

  [M（N 2）2（dppe）2 ]的反应[M = MO或W; dppe = 1,2-双（二苯基膦基乙烷）与烷基溴化物，酰氯或芳酰氯，在辐射下会形成有机肼基（2-）-和有机二氮杂烯基复合物。配合物[ReCl（N 2）（PMe 2 Ph）4 ]和[ReCl（N 2）（py）（PMe 2 Ph）3 ]（py =吡啶）可被酰化但不能在二氮处烷基化，但可在[OsCl 2（N 2）（PMe 2 Ph）4]二氮即使对酰基氯也没有活性。氮在其配合物中的反应性沿第三过渡系列以W> Re> Os的顺序降低。

  DOI：

  10.1039/dt9770000688
• 作为产物：
  描述：

  Re(O)(OEt)(PPh3)2Br3 、 苯甲酰肼 、 三苯基膦 以 乙醇 、 氢溴酸 为溶剂， 以73%的产率得到[benzoylhydrazido(3-)-ON']dibromobis(triphenylphosphine)rhenium(V)
  参考文献：
  名称：

  Rhenium(I) Terpyridine π-Bases:  Reversible η²-Coordination of Ketones, Aldehydes, and Olefins in the Terpyridine Plane

  摘要：

  The complex trans-[Re(terpy)(Br)(PPh3)(2)][OTf] (2) (terpy = 2,2':6',2"-terpyridine) is a convenient precursor to the electron-rich pi-basic fragment {(terpy)(L)(2)Re}(+) (L = (BuNC)-Bu-t or PMe3). Reduction of 2 with activated magnesium in the presence of unsaturated organic molecules and an excess of either tBuNC or PMe3 yields complexes of the type trans-[(terpy)(L)(2)Re(eta(2)-pi)][OTf] (L = (BuNC)-Bu-t or PMe3; pi = olefin, aldehyde, or ketone), The dihapto-coordinated organic moieties show a preference for binding in the plane of the terpy ligand. Reaction of trans- [Re(terpy)((BuNC)-Bu-t)(2)(eta(2)-acetone)][OTf] (9) with MeOTf yields an observable mu(2)-ketonium complex, The electronic environment of these complexes has been probed by cyclic voltammetry, and the details of ligand exchange for the eta(2)-ketone complexes are presented. Geometric features determined from X-ray crystal structure analyses of trans-[(terpy)((BuNC)-Bu-t)(2)Re(eta(2)-cyclopentene)][OTf] (4) and trans-[(terpy)((BuNC)-Bu-t)(2)Re(eta(2)-acetophenone)][OTf] (11) are reported.

  DOI：

  10.1021/om980500p

文献信息

• The cleavage of the NN bond of N,N-disubstituted hydrazines on rhenium. The preparation, reactions and x-ray crystal structures of [ReCl2(NH3)(NNCOC6H4-4-R)(PPh3)2] (R = H, OMe, NO2), [ReCl3(NNPh2)(PPh3)2], [ReCl2(N)(NNPh2)(PPH3)] and [ReCl(N)(Me2CNNCOPh)(PPh3)2]
  作者：Jonathan R. Dilworth、Panna Jobanputra、John R. Miller、Suzanne J. Parrott、Qin Chen、Jon Zubieta

  DOI：10.1016/s0277-5387(00)83403-8

  日期：1993.3

  Reaction of the N,O-chelated complexes [ReCl2(N2COC6H4-4-R)(PPh3)2] (R = H, Me, NO2) with N,N- and certain N-substituted hydrazines gave the ammine complexes [ReCl2(NH3)(NNCOC6H4-4-R)(PPh3)2] [R = H (1), R = Me (2), R = NO2 (3)]. The mechanism is believed to involve intermolecular homolytic cleavage of the N-N bond. The X-ray structure of 1 revealed a pseudo-octahedral geometry with trans-phosphines. The ammine ligand is cis to the benzoyldiazenido group and the ammine hydrogens are hydrogen-bonded to the carbonyl oxygen.Reaction of [ReOCl3(PPh3)2] with excess Ph2NNH2.HCl in ethanol gave both [ReCl3(NNPh2)(PPh3)2] (6) and [ReCl2(N)(NNPh2)(PPh3)] (7). In the presence of base the rhenium(VII) cation [ReCl2(NNPh2)2(PPh3)+ was formed. The geometry of 7 was shown by X-ray structural determination to be a distorted square-based pyramid, with the nitride in the apical position. Attempted derivatization of 7 led to N-N bond cleavage and the generation of nitrido complexes.The nitrido complex [ReCl(N)(Me2CNNCOPh)(PPh3)2] (8) was unexpectedly formed in the reaction of [ReOCl3(PPh3)2] with Me2C=NNHCOPh in ethanol in the presence of HCl. The X-ray crystal structure of 8 showed a pseudo-octahedral geometry with the nitride ligand trans to the oxygen of the N,O-chelated hydrazonato(1-) ligand. The possible mechanisms of N-N bond cleavage are discussed.
• Synthesis, spectroscopic investigation, structural characterization and DFT calculation of the complexes [ReX2(N2COPh)(4-PhPyr)(PPh3)2] (X=Cl,Br)
  作者：S. Michalik、B. Machura、R. Kruszynski、J. Kusz、M. Krompiec

  DOI：10.1016/j.poly.2010.06.015

  日期：2010.9

  The reactions of [ReX2(eta(2)-N2COPh-N',O)(PPh3)(2)] with 4-phenylpyrimidine have been performed. As a result, the two complexes [ReX2(N2COPh)(4-PhPyr)(PPh3)(2)] (X = Cl, Br) (4-PhPyr = 4-phenylpyrimidine), isostructural in the solid state, have been obtained. The crystal and molecular structures of ([ReCl2(N2COPh)(4-PhPyr)(PPh3)(2)])(2)center dot CHCl3 (1) and ([ReBr2(N2COPh)(4-PhPyr)(PPh3)(2)])2 center dot CHCl3 (2) have been determined. The electronic structure of [ReCl2(N2COPh)(4-PhPyr)(PPh3)(2)] has been examined using the density functional theory (DFT) method. The spin-allowed electronic transitions of 1 have been calculated with the time-dependent DFT method, and the UV-Vis spectrum of [ReCl2(N2COPh)(4-PhPyr)(PPh3)(2)] has been discussed on this basis. (C) 2010 Elsevier Ltd. All rights reserved.