铼,三溴羰基二(三苯基胂)- | 19271-56-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: 铼,三溴羰基二(三苯基胂)-
• 中文别名: 铼,三溴羰基二(三苯基胂)-
• 英文名称: Rhenium, tribromooxobis(triphenylarsine)-
• 英文别名: [ReOBr3(triphenylarsine)2]；[ReOBr3(AsPh3)2]；[ReOBr(AsPh3)2]；ReOBr3(AsPh3)2；ReOCl3(AsPh3)2
• CAS: 19271-56-8；136173-40-5
• 化学式: C₃₆H₃₀As₂Br₃ORe
• 分子量: 1054.4
• InChiKey: QVFRSVOYPAAXNU-UHFFFAOYSA-K

计算性质

• 辛醇/水分配系数(LogP)：
  6.82
• 重原子数：
  43.0
• 可旋转键数：
  8.0
• 环数：
  6.0
• 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：

  铼,三溴羰基二(三苯基胂)- 、 顺-1,2-双(二苯基膦)乙烯 以 二氯甲烷 为溶剂， 以44%的产率得到
  参考文献：
  名称：

  New complexes of rhenium-(V) or -(III) with various diphosphines or bis(diphenylphosphino)methane monoxide: crystal structure of mer-[ReCl₃(dppm-PP′)(dppom-P)][dppm = Ph₂PCH₂PPh₂, dppom = Ph₂PCH₂P(O)Ph₂]

  摘要：

  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.

  DOI：

  10.1039/dt9910001519
• 作为产物：
  描述：

  铼 、 三苯胂 在 H₂O₂ 、 HBr 作用下， 以 溶剂黄146 为溶剂， 以81%的产率得到铼,三溴羰基二(三苯基胂)-
  参考文献：
  名称：

  New complexes of rhenium-(V) or -(III) with various diphosphines or bis(diphenylphosphino)methane monoxide: crystal structure of mer-[ReCl₃(dppm-PP′)(dppom-P)][dppm = Ph₂PCH₂PPh₂, dppom = Ph₂PCH₂P(O)Ph₂]

  摘要：

  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.

  DOI：

  10.1039/dt9910001519

文献信息

• Oxidorhenium( <scp>V</scp> ) Complexes of a Family of Bipyridine‐Like Ligands Including Pyridyltriazines and Pyrazinyltriazine: Oxygen‐Atom Transfer, Metal Redox and Correlations
  作者：Samir Das、Animesh Chakravorty

  DOI：10.1002/ejic.200501102

  日期：2006.6

  derivatives, phenanthroline (phen), 5,6-diphenyl-3-(2-pyridyl)-1,2,4-triazine (ppyt) and its dimethyl (mpyt) and pyrazinyl (ppzt) analogues. The concerned oxido complexes are [ReOCl3(L)],[ReOBr3(ppyt)] and [ReOBr3(ppzt)]. The chloro and bromo complexes of ppyt and ppzt were prepared by reacting these ligands with [ReOX3(AsPh3)2] (X = Cl, Br). The X-ray structures of [ReOCl3(ppyt)] and [ReOCl3(ppzt)] reveal

  标题配体（通用缩写L）为联吡啶（bpy）、其二甲基（mbpy）和二苯基（pbpy）衍生物、菲咯啉（phen）、5,6-二苯基-3-（2-吡啶基）-1,2,4 -三嗪 (ppyt) 及其二甲基 (mpyt) 和吡嗪基 (ppzt) 类似物。相关的氧化配合物是[ReOCl3(L)]、[ReOBr3(ppyt)]和[ReOBr3(ppzt)]。ppyt 和 ppzt 的氯和溴配合物是通过这些配体与 [ReOX3(AsPh3)2] (X = Cl, Br) 反应制备的。[ReOCl3(ppyt)] 和 [ReOCl3(ppzt)] 的 X 射线结构表明 ReCl3 片段是经向排列的，L 配体是 N,N 配位的，因此吡啶/吡嗪氮与氧化氧原子。Re-O 长度 [1.656(10)/1.625(9) A] 对应于近似的三键。氧原子从溶液中的 [ReOX3(L)] 转移到三苯基膦的速率遵循二级动力学，并与大的负活化熵（约
• Reactivity of [ReOX3(AsPh3)2] (X=Cl, Br) complexes towards gaseous nitric oxide.
  作者：B Machura、J.O Dzięgielewski、S Michalik、T.J Bartczak、R Kruszynski、J Kusz

  DOI：10.1016/s0277-5387(02)01254-8

  日期：2002.12

  Abstract The reactions of the complexes [ReOX 3 (AsPh 3 ) 2 ] (X=Cl, Br) with gaseous nitric oxide and the reactions of the compounds [NBu 4 ] 2 [ReX 5 (NO)] (X=Cl, Br) with an excess of triphenylarsine have been examined. [ReOBr 3 (AsPh 3 ) 2 ] reacts with nitric oxide to give mer , cis -[ReBr 3 (NO)(OAsPh 3 ) 2 ] ( 1 ), whereas the reaction of the chlorine oxocomplex with NO leads to three products: [ReCl

  摘要配合物[ReOX 3（AsPh 3）2]（X = Cl，Br）与气态一氧化氮的反应以及化合物[NBu 4] 2 [ReX 5（NO）]（X = Cl，Br ）中已检测到过量的三苯ar。[ReOBr 3（AsPh 3）2]与一氧化氮反应生成顺式-[ReBr 3（NO）（OAsPh 3）2]（1），而氯氧络合物与NO的反应生成三种产物：[ ReCl 3（NO）（OAsPh 3）2]（2），mer，反式-[ReCl 3（NO）（AsPh 3）2] [ReCl 4（AsPh 3）2]（3）和顺式-[ReCl 4（ OAsPh 3）2]（4）。化合物[NBu 4] 2 [ReX 5（NO）]（X = Cl，Br）与过量的AsPh 3反应生成3和mer，反式-[ReBr 3（NO）（AsPh 3）2]（5 ）， 分别。在这些反应中获得的络合物已通过红外，紫外-可见和磁测量进行了表征。已经确定了配合物1和3
• Reactivity of oxorhenium(V) complexes towards 8-hydroxyquinoline-2-carboxylic acid: X-ray structure of [ReOCl2(hquin-2-COOH)(AsPh3)]·MeCN and [ReOCl2(hquin-2-COOH)(PPh3)]·MeCN complexes. DFT and TDDFT calculations for [ReOCl2(hquin-2-COOH)(AsPh3)]
  作者：B. Machura、J. Kusz

  DOI：10.1016/j.poly.2007.09.019

  日期：2008.1

  The reactions of [ReOX3(EPh3)(2)] with 8-hydroxyquinoline-2-carboxylic acid (Hhquin-2-COOH) have been examined and [ReOX2-(hquin-2-COOH)(EPh3)]center dot MeCN (X = Cl, Br; E = As, P) complexes have been obtained. All the complexes were characterised by IR, U-V-Vis spectroscopy and elemental analysis. The crystal and molecular structures have been determined for [ReOCl2(hquin-2-COOH)(AsPh3)]center dot MeCN and [ReOCl2(hquin-2-COOH)(PPh3)]center dot MeCN. The electronic structure of [ReOCl2(hquin-2-COOH)(AsPh3)] has been calculated with the density functional theory (DFT) method, and TDDFT calculations have been employed to produce a hundred of singlet excited-states starting from the ground-state geometry optimized in the gas phase. (C) 2007 Elsevier Ltd. All rights reserved.
• 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.
• Novel oxorhenium complex of 4,5-diaza-fluoren-9-one-synthesis, spectroscopic characterization, X-Ray structure and DFT calculations
  作者：B. Machura、M. Wolff、A. Świtlicka

  DOI：10.1016/j.inoche.2010.09.017

  日期：2011.1

  The paper presents a combined experimental and computational study of the dinuclear oxorhenium(V) complex incorporating 4,5-diaza-fluoren-9-one (dafone). The complex has been studied by IR, UV-vis spectroscopy and X-ray crystallography. The electronic structure of [Re2O3Br4(dafone)(2)] has been calculated with the density functional theory (DFT) method, and the electronic spectrum of the complex was investigated at the TDDFT level employing B3LYP functional in combination with LANL2DZ. (C) 2010 Elsevier B.V. All rights reserved.