cis-oxotrichloro(cis-1,2-bis(diphenylphosphino)ethylene)rhenium(V) | 127593-07-1

• 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: cis-oxotrichloro(cis-1,2-bis(diphenylphosphino)ethylene)rhenium(V)
• 英文别名: fac-[ReOCl3(bis(diphenylphosphino)ethene)]；fac-[ReOCl3(dppen)]
• CAS: 127593-07-1；74679-92-8
• 化学式: C₂₆H₂₂Cl₃OP₂Re
• 分子量: 704.974
• InChiKey: GPDNIVRAIVQMOY-CSVSGXLVSA-K

计算性质

• 辛醇/水分配系数(LogP)：
  7.67
• 重原子数：
  33.0
• 可旋转键数：
  4.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  17.07
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  cis-oxotrichloro(cis-1,2-bis(diphenylphosphino)ethylene)rhenium(V) 、 sodium tetrahydroborate 以 乙醇 为溶剂， 生成 cis-1,2-bis(diphenylphosphino)ethylene heptahydrido rhenium(VII)
  参考文献：
  名称：

  New multihydride complexes of rhenium containing diphosphine ligands: low-temperature protonation of [ReH₇(Ph₂PCHCHPPh₂-PP′)]

  摘要：

  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.

  DOI：

  10.1039/dt9940000917
• 作为产物：
  描述：

  mer-[ReOCl3(SMe2)(OPPh3)] 、 1,2-bis(diphenylphosphino)ethylene 以 四氢呋喃 为溶剂， 以44%的产率得到cis-oxotrichloro(cis-1,2-bis(diphenylphosphino)ethylene)rhenium(V)
  参考文献：
  名称：

  Oxo-rhenium(V) complexes with analogs of bis(diphenylphosphino)ethane

  摘要：

  Compounds of the types ReOCl3(L-L) and ReOCl2(OEt)(L-L) with bis(diphenylphosphino)ethene (dppen) and bis(diphenylphosphino)ferrocene (dppf) were prepared by reacting the diphosphine with ReOCl3(OPPh3)(Me2S). The ReOCl3(L-L) compound with bis(diphenylarsino)ethane (dpae) was prepared similarly. Crystallographic work on ReOCl3(dppen) and ReOCl3(dpae) confirmed the approximate octahedral environment of the metal and the presence of a Cl ligand traits to the Re=O bond. The ReOCl2(OEt)(L-L) compounds contain a transO=Re-OEt unit. The visible spectra of both types of compounds include a two-component d-d absorption pattern originating from the spin-allowed excitation of a d electron from the interaxial d orbital in the equatorial plane to the empty d(xz) and d(yz) orbitals. For ReOCl2(OEt)(dppf), these bands are masked by strong transitions taking place in the ferrocene moiety. The absorptions of the other systems are not greatly displaced compared to the similar dppe compounds, a small decrease in the transition energy being noted for the dpae complex. (c) 2005 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.ica.2005.07.038

文献信息

• Synthesis and structural studies of some new rhenium phosphine heptahydride complexes. Evidence for classical structures in solution
  作者：Xiao Liang Luo、Robert H. Crabtree

  DOI：10.1021/ja00168a028

  日期：1990.6

  phosphine heptahydride complexes ReHsub 7}Lsub 2} (Lsub 2} = a chelating bidentate phosphine) have been synthesized and characterized by IR and sup 1}H, and sup 31}P, and sup 13}C NMR spectroscopy. The hydride resonances of ReHsub 7}(dppf) (1, dppf = 1,1prime}-bis(diphenylphosphino)ferrocene), ReHsub 7}(dppb) (2, dppb = 1,4-bis(diphenylphosphino)butane), and ReHsub 7}((+)-diop) (3, (+)-diop = (4S

  合成了一系列新的铼膦七氢化物配合物 ReHsub 7}Lsub 2}（Lsub 2} = 螯合双齿膦）并通过 IR 和 sup 1}H 和 sup 31}P 表征，和sup 13}C NMR光谱。ReHsub 7}(dppf) (1, dppf = 1,1prime}-bis(diphenylphosphino)ferrocene), ReHsub 7}(dppb) (2, dppb = 1,4-bis(二苯基膦基)丁烷)和ReHsub 7}((+)-diop) (3, (+)-diop = (4S,5S)-4,5-双((二苯基膦基)甲基)-2,2-二甲基-1,3-二氧戊环）在冷却时发生脱聚。低温氢化物图案表明经典的 9 坐标三端三棱柱结构。与经典结构一致，
• 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.