bis(dimethylphenylphosphine)nickel(II) bromide | 19615-77-1

• 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: bis(dimethylphenylphosphine)nickel(II) bromide
• 英文别名: NiBr2(dimethylphenylphosphine)2；dibromonickel;dimethyl(phenyl)phosphane
• CAS: 19615-77-1；25456-40-0
• 化学式: C₁₆H₂₂Br₂NiP₂
• 分子量: 494.796
• InChiKey: PHSMAXWMZORZFF-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  5.8
• 重原子数：
  21.0
• 可旋转键数：
  4.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  bis(dimethylphenylphosphine)nickel(II) bromide 在 (C₅H₅)Na 作用下， 以 四氢呋喃 为溶剂， 生成
  参考文献：
  名称：

  Cyclopentadienylbis(ligand)nickel(I): synthesis and characterization, including the x-ray structure of .eta.5-cyclopentadienyl-1,1'-bipyridylnickel(I). Observations on the mechanism of substitution of nickelocene

  摘要：

  DOI：

  10.1021/ja00410a044
• 作为产物：
  描述：

  nickel(II) bromide trihydrate 、 二甲基苯基磷 以 乙醇 为溶剂， 反应 0.5h， 以95%的产率得到bis(dimethylphenylphosphine)nickel(II) bromide
  参考文献：
  名称：

  从空气稳定镍 (II) 配合物进入均质镍 (0) 催化剂的广泛适用策略

  摘要：

  已经合成了一系列 L 2 Ni（芳基）X（L = 单齿膦，X = Cl，Br）和 LNi（芳基）X（L = 双膦）形式的空气稳定镍配合物，并表示为适用于各种镍催化转化的预催化剂库。这些配合物很容易由低成本的 NiCl 2 ·6H 2 O 或 NiBr 2 ·3H 2合成O 和所需的配体，然后加入 1 当量的格氏试剂。选择的这些配合物通过单晶 X 射线衍射进行了表征，并提供了对其结构特征的分析。介绍了将它们用作镍催化羰基-烯反应的预催化剂的案例研究，与使用 Ni(cod) 2 的反应相比，显示出优异的反应性。此外，由于预催化剂都对空气稳定，因此不需要手套箱或惰性气氛技术来利用这些配合物进行镍催化反应。

  DOI：

  10.1021/om500156q
• 作为试剂：
  描述：

  一氧化碳 、 水 在 bis(dimethylphenylphosphine)nickel(II) bromide 作用下， 以 乙醇 、 水 为溶剂， 生成 二氧化碳 、 氢气
  参考文献：
  名称：

  NiX 2-叔膦体系对水煤气变换反应的均相催化

  摘要：

  所述NIX 2大号2（X =氯，溴; L = PME 3 PET 3 PBut 3，P（I-PR）3，PME 2 PH，PET 2 PH）水-醇溶液，催化水煤气变换反应（WGSR ），一氧化碳，大气压和高于90°C的温度。该催化作用通过以下主要反应完成：NiX 2 L 2 + 3CO + H 2 O→Ni（CO）2 L 2 + 2HX + CO 2；Ni（CO）2 L 2 + 2HX + CO 2；Ni（CO）2 L 2 + 2HX + CO 2。Ni（CO）2 L 2 + 2HX→NiX 2 L 2 + H2，也可以单独进行。催化活性随时间缓慢降低，顺序为：PR 3

  DOI：

  10.1016/s0020-1693(00)87578-7

文献信息

• Coordination chemistry of higher oxidation states Part 9 [1]. Nickel(III) complexes of monodentate phosphines and related ligands
  作者：Simon J. Higgins、William Levason、Deborah J. Wilkes

  DOI：10.1016/s0020-1693(00)87660-4

  日期：1984.4

  The known nickel(III) complexes [Ni(PR3)2X3]) (X = Cl, Br) with monodentate phosphines (PMe3, PEt3, PnBu3, PMe2Ph X = Br only) have been reexamined, some being obtaines in a pure state for the first time. New complexes with PMe2Ph, PEt2Ph and PMePh2 are described. Detailed spectroscopic data (IR, UV/Visible and EPR) are reported and assigned for all complexes, leading to the proposal of trans-trigonal

  已知镍（III）配合物[镍（PR 3）2 X 3 ]）（X =氯，溴）与单齿膦（PME 3， PET 3，P Ñ卜3，PME 2博士X只为Br）已经重新审查，有些是第一次获得纯净状态。与PME新复合物2 PH，PET 2 h和PMePh 2描述。报告了所有配合物的详细光谱数据（IR，UV / Visible和EPR）并进行了分配，从而提出了跨三角双锥体结构（D 3h）的建议，以证明P（OMe）的镍（III）配合物在溶液中形成）3，AsEt 3，PCy 3（Cy =环己基），PPh 3也被给出。讨论了影响这些配合物稳定性的因素。
• [EN] NICKEL PRE-CATALYSTS AND RELATED COMPOSITIONS AND METHODS<br/>[FR] PRÉ-CATALYSEURS DE NICKEL ET COMPOSITIONS ET MÉTHODES ASSOCIÉES
  申请人：MASSACHUSETTS INST TECHNOLOGY

  公开号：WO2015070026A1

  公开（公告）日：2015-05-14

  Described herein are nickel pre-catalysts and related compositions and methods. The nickel pre-catalysts may be activated to form catalysts which may be utilized in organic reactions.

  本文描述了镍前催化剂及相关组成物和方法。这些镍前催化剂可以被活化形成催化剂，可用于有机反应中。
• Inorganic Grignard analogues. Reaction of cobalt powder with triorganodiiodophosphorus compounds to form [PR3I][Co(PR3)I3]. Crystal structure of [PPh3I][Co(PPh3)I3], and isolation of the novel complexes [PPh3I][Co(PPh3)IBr2] and [SbPh3I][Co(SbPh3)I3]
  作者：Stephen M. Godfrey、Helen P. Lane、Charles A. McAuliffe、Robin G. Pritchard

  DOI：10.1039/dt9930001599

  日期：——

  The reactions of a large number of triorganodiiododophosphorus compounds, R3PI2 [R3 = Et3, Pr(n)3, Bu(n)3, PhMe2, Ph2Me, Ph2Pr(n), Ph3 (o-,m- or p-MeC6H4)Ph2, or (m-MeC6H4)3], with unactivated cobalt metal in dry diethyl ether have been studied. All reactions produce the novel ionic complexes [PR3I][Co(PR3)I3] in quantitative yield, illustrated crystallographically for [PPh3I][Co(PPh3)I3]. However, where R3 = PhMe2 both the ionic complex and the cobalt(III) complex [Co(PPhMe2)2I3] are produced from the same reaction. The previously reported isolation of the 'frozen transition-state complex' [Co(PBun3)3I8] from the reaction of Bun3PI2 with cobalt powder has been reinvestigated; when allowed to proceed to completion, the reaction produces the ionic complex described above. The compound Ph3PIBr reacts with cobalt powder to produce the mixed-halide ionic complex [PR3I][Co(PR3)IBr2]. All the complexes [PR3I][Co(PR3)I3] have been studied using Raman and visible spectroscopy, the latter confirming the tetrahedral geometry of the cobalt anion. Very little reaction is observed with the corresponding dibromophosphorus compounds, R3PBr2, but in some cases visible spectroscopic studies on the trace of complex formed suggest a tetrahedral cobalt(II) species, perhaps similar to the iodo-complexes described above. Additionally, Ph3SbI2 reacts with cobalt metal in an analogous way to Ph3PI2 to produce the novel complex [SbPh3I][Co(SbPh3)I3].
• Inorganic grignard analogues. Reaction of nickel powder with dihalogenotriorganophosphorus compounds to form nickel-(II) and -(III) phosphine complexes; isolation of planar [Ni(PPh3)I3]? and the crystal structure of [Ni(PPhMe2)2Br2]
  作者：Stephen M. Godfrey、Charles A. McAuliffe、Robin G. Pritchard

  DOI：10.1039/dt9930002875

  日期：——

  Reactions of dihalogenotriorganophosphorus compounds R3PX2 (X = Br or I) with unactivated coarse-grain nickel metal powder have been investigated. The nature of the nickel phosphine complexes formed is remarkably dependent on both R and X. Where R not-equal Me and X = I the nickel(II) complexes [R3PI] [Ni(PR3)I3] are formed, analogous to, but not isostructural with, similar cobalt complexes of the same stoichiometry formed from cobalt powder and R3PI2. Quantitative electronic spectroscopic studies indicated that, surprisingly, the [R3PI][Ni(PR3)I3] complexes all have predominantiy square-planar geometry around nickel. Where R = Me and X = 1, the nickel(III) complex [Ni(PMe3)2I3] is obtained in quantitative yield, the other product being diiodine. Reaction of nickel powder with Me2PhPI2 yields both the nickel(II) complex, [MePhPI][Ni(PPhMe2)I3], and the nickel(III) complex, [Ni(PPhMe2)2I3]. These observations again mirror analogous cobalt reactions. Reaction of the analogous dibromo compounds, R3PBr2, with nickel powder is extremely sensitive to the nature of R. Where R = Me, Et or Pn(n) no reaction occurs; where R3 = PhMe2 the square-planar complex [Ni(PPhMe2)2Br2] and an octahedral complex of stoichiometry Ni(PPhMe2)2Br, are obtained in equal yield. Where R3 = Ph2Pr(n) the octahedral complex [Ni(PPh2Prn)2Br4] is formed with a trace of the planar complex [Ni(PPh2Prn)2Br2], and where R = Ph the octahedral complex [Ni(PPh3)2Br4] is formed in quantitative yield. The complex [Ni(PPhMe2)2Br] has been crystallographically characterised: monoclinic, space group P2(1)/a, a = 10.018(2), b = 10.249(1), c = 10.138(1) angstrom and Z = 2 (molecule centrosymmetric).
• Kukushkin, Yu. N.; Sedova, G. N.; Aleshin, V. E., Russian Journal of Inorganic Chemistry, <hi>1980</hi>, vol. 25, p. 424 - 425
  作者：Kukushkin, Yu. N.、Sedova, G. N.、Aleshin, V. E.、Ageeva, E. D.、Avetikyan, G. B.

  DOI：——

  日期：——