氧化三氯[双(二苯基膦)甲烷]铼(V) | 60260-17-5

• 中文名称: 氧化三氯[双(二苯基膦)甲烷]铼(V)
• 英文名称: ReOCl₃(dppm)
• 英文别名: fac-{ReOCl3(dppm-P,P')}
• CAS: 60260-17-5
• 化学式: C₂₅H₂₂Cl₃OP₂Re
• 分子量: 692.963
• InChiKey: SAVOOVLDSRTAGJ-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：
  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

安全信息

• WGK Germany：
  3

反应信息

• 作为反应物：
  描述：

  双二苯基膦基甲基二苯基氧化膦 、 氧化三氯[双(二苯基膦)甲烷]铼(V) 以 氯仿 为溶剂， 生成 mer-{ReCl3(dppm-P,P')(dppom-P)}
  参考文献：
  名称：

  含有不同核如[ReO] 3 +，[ReNR] 3+和[ReN] 2+的rh（V）配合物对双（二苯基膦基）甲烷的反应性：合成和晶体结构

  摘要：

  配合物fac- [ReOCl3（dppm-P，P'）]（1a），mer- [ReOCl3（dppm-P，P'）]（1b），mer- [ReCl3（dppm-P，P'）（dppom） -P）]（2），[ReCl4（dppom-P，O）]（3）和mer- [ReCl3（dppm-P，P'）PPh3]（4）（dppmPh2PCH2PPh2，dppomPh2PCH2P（O） ）Ph2）是通过[ReOCl3（PPh3）2]或[AsPh4] [ReOCl4]与dppm在不同的实验条件下反应获得的。配合物1b可能是通过配合物2或4的中间形成而获得的。配合物fac- [Re（NCH3）Cl3（dppm-P，P']（5），反式-[ReNCl2（dppm-P）PPh3]（6 ）和[ReNCl（dppm-P，P'）2] Cl（7）也分别从[Re（NCH3）Cl3（PPh3）2]和[ReNCl2（PPh3）2]开始获得。

  DOI：

  10.1016/s0020-1693(00)88114-1
• 作为产物：
  描述：

  [ReOCl₃(PPh₃)₂] 、 双二苯基膦甲烷 以 氯仿 为溶剂， 以85%的产率得到氧化三氯[双(二苯基膦)甲烷]铼(V)
  参考文献：
  名称：

  含有不同核如[ReO] 3 +，[ReNR] 3+和[ReN] 2+的rh（V）配合物对双（二苯基膦基）甲烷的反应性：合成和晶体结构

  摘要：

  配合物fac- [ReOCl3（dppm-P，P'）]（1a），mer- [ReOCl3（dppm-P，P'）]（1b），mer- [ReCl3（dppm-P，P'）（dppom） -P）]（2），[ReCl4（dppom-P，O）]（3）和mer- [ReCl3（dppm-P，P'）PPh3]（4）（dppmPh2PCH2PPh2，dppomPh2PCH2P（O） ）Ph2）是通过[ReOCl3（PPh3）2]或[AsPh4] [ReOCl4]与dppm在不同的实验条件下反应获得的。配合物1b可能是通过配合物2或4的中间形成而获得的。配合物fac- [Re（NCH3）Cl3（dppm-P，P']（5），反式-[ReNCl2（dppm-P）PPh3]（6 ）和[ReNCl（dppm-P，P'）2] Cl（7）也分别从[Re（NCH3）Cl3（PPh3）2]和[ReNCl2（PPh3）2]开始获得。

  DOI：

  10.1016/s0020-1693(00)88114-1
• 作为试剂：
  描述：

  1-phenylhept-2-yn-1-ol 、 双丙酮半乳糖 在 氧化三氯[双(二苯基膦)甲烷]铼(V) 作用下， 以 乙腈 为溶剂， 反应 10.0h， 以60%的产率得到(3aR,5R,5aS,8aS,8bR)-2,2,7,7-Tetramethyl-5-(1-phenyl-hept-2-ynyloxymethyl)-tetrahydro-bis[1,3]dioxolo[4,5-b;4',5'-d]pyran
  参考文献：
  名称：

  由铼-氧配合物催化的温和的 C−O 键形成

  摘要：

  描述了一种通过炔丙醇与一系列其他醇偶联来区域选择性合成炔丙醚的温和方法。该方法使用耐空气和耐湿的铼-氧配合物 ((dppm)ReOCl3) 作为形成 sp3-碳-氧键的催化剂，而无需事先活化炔丙醇或去质子化醇亲核试剂。允许使用范围广泛的官能团，包括芳基卤化物、烯烃、酯和酸不稳定官能团，例如缩醛。此外，即使在其他亲电子试剂如伯烷基卤化物和共轭酯存在的情况下，也优先发生醇的置换。

  DOI：

  10.1021/ja0343050

文献信息

• Catalytic deoxydehydration of glycerol to allyl alcohol in the presence of mono-oxygenated rhenium diphosphine complexes
  作者：Mehrnaz Aliahmadi、Ali Nemati Kharat、Jan Janczak

  DOI：10.1016/j.poly.2023.116734

  日期：2024.1

  complexes as catalysts and alcohol as the solvent and hydrogen transfer agent. Among the tested complexes, the [ReOBr3(Xantphos)] complex combined with 2-propanol as a solvent and the reducing agent exhibited the most outstanding performance, yielding allyl alcohol with an exceptional efficiency of 100%. The structures of three newly synthesized complexes, [ReOBr3(Xantphos)], [ReOBr3(DPEphos)], and [ReOCl3(dppb)]

  尽管存在环境问题，但烯丙醇是合成由石油衍生的丙烯工业生产的高分子化合物的重要有机中间体。在这项研究中，我们提出了一种利用具有成本效益且可再生的生物资源甘油作为起始材料的系统。在这方面，我们在单氧化铼二膦配合物作为催化剂、醇作为溶剂和氢转移剂的存在下进行了该反应。在测试的配合物中，[ReOBr 3 (Xantphos)]配合物与2-丙醇作为溶剂和还原剂结合表现出最突出的性能，以100%的优异效率产生烯丙醇。通过X射线单晶分析确定了三种新合成的配合物[ReOBr 3 (Xantphos)]、[ReOBr 3 (DPEphos)]和[ReOCl 3 (dppb)]的结构。这些发现有助于推动烯丙醇生产的进步，为传统的石油基方法提供更可持续、更环保的替代方案。
• 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.
• New multihydride complexes of rhenium containing diphosphine ligands: low-temperature protonation of [ReH₇(Ph₂PCHCHPPh₂-PP′)]
  作者：Xavier L. R. Fontaine、Timothy P. Layzell、Bernard L. Shaw

  DOI：10.1039/dt9940000917

  日期：——

  Treatment of oxochloro complexes of tge type (ReOCl3(L-L)] (L-L = diphosphine) with sodium tetrahydroborate gave complexes of the type [ReH7(L-L)]. Treatment of [ReH7(dppen-PP)] la [dppen = cis-1,2-bis(diphenylphosphino)ethylene = cis-Ph2PCH=CHPPh2] with triphenylphosphine gave a mixture of the pentahydride [ReH5(dppen-PP)(PPh3)] and the trihydride (ReH3(dppen-PP')(PPh3)2]. However, treatment of la with dppm [bis(diphenylphosphino)methane, Ph2PCH2PPh2] in refluxing toluene, followed by slow crystallisation, gave [ReH5(dppen-PP)(dppm-P)] which was isolated and characterised by variable-temperature NMR spectroscopy. Prolonged heating of la with dppm gave the trihydride [ReH3(dppen-PP)(dppm-PP)], the fluxionality of which was studied by NMR spectroscopy between +90 and -70-degrees-C. Protonation of la with HBF4.Et2O, at -80-degrees-C, gave a complex formulated as [ReH6(eta2-H-2)(dppen-PP)]+ which, on warming to ambient temperature, was cleanly converted to a dirhenium multihydride species tentatively formulated as [(dppen-PP')H3Re(mu-H)2-ReH3(dppen-PP')] on the basis of IR and NMR evidence.