[(dtbpe)Ni(μ-Cl)]₂ | 345893-98-3

• 分子结构分类: 有机化合物 - 有机磷化合物 - 有机膦及其衍生物
• 英文名称: [(dtbpe)Ni(μ-Cl)]₂
• 英文别名: [(1,2-tBu₂PCH₂CH₂PtBu₂)Ni(μ-Cl)]₂；chloro(1,2-bis(di-tert-butylphosphino)ethane)nickel(I) dimer；[(dtbpe)NiCl]2；[(1,2-bis(di-tert-butylphosphino)ethane)NiCl]2；[(1,2-bis(di-tert-butylphosphino)ethane)Ni(μ-Cl)]2；[(Ni(μ-Cl)(dtbpe))2]；[Ni2Cl2(dtbpe)2]；chloronickel;ditert-butyl(2-ditert-butylphosphanylethyl)phosphane
• CAS: 345893-98-3
• 化学式: C₃₆H₈₀Cl₂Ni₂P₄
• 分子量: 825.212
• InChiKey: QWNWDWULSNGRTG-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：

  [(dtbpe)Ni(μ-Cl)]₂ 在 NaN(TMS)2 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 生成 [(1,2-bis(di-tert-butylphosphino)ethane)Ni(CH2CMePhCH2)]
  参考文献：
  名称：

  Preparation of Stable Alkyl Complexes of Ni(I) and Their One-Electron Oxidation to Ni(II) Complex Cations

  摘要：

  The three-coordinate nickel(I) alkyl complexes (dtbpe)Ni(CH2CMe3) (2), (dtbpe)Ni(CH2SiMe3) (3), and (dtbpe)Ni(CH2CMe2Ph) (4) have been prepared by treatment of [(dtbpe)NiCl]2 with alkyllithium reagents. While thermally robust, they each undergo mild one-electron oxidation to give the corresponding Ni(II) complex cations [(dtbpe)Ni(CH2CMe3)+] (5), [(dtbpe)Ni(CH2SiMe3)+] (6), and [(dtbpe)Ni(CH2CMe2Ph)+] (7) as red-brown [PF6-] or [BArF4-] salts. In contrast to cationic amido and phosphido analogues that undergo alpha-deprotonation to afford imido and phosphinidene derivatives, deprotonation of 5-7 occurs at a gamma-CH3 group to give metallacyclobutane products (dtbpe)Ni(CH2CMe2CH2) (8), (dtbpe)Ni(CH2SiMe2CH2) (9), and (dtbpe)Ni(CH2CPhMeCH2) (10), not (dtbpe)Ni=CHR.

  DOI：

  10.1021/ja047052z
• 作为产物：
  描述：

  (dtbpe)NiCl2 在 KC₈ 作用下， 以 四氢呋喃 为溶剂， 以73%的产率得到[(dtbpe)Ni(μ-Cl)]₂
  参考文献：
  名称：

  Synthesis of 1,2-bis(di-tert-butylphosphino)ethane (dtbpe) complexes of nickel: radical coupling and reduction reactions promoted by the nickel(I) dimer [(dtbpe)NiCl]2

  摘要：

  Tetrahydrofuran solutions of (dtbpe)NiCl2 (dtbpe = 1,2-bis(di-tert-butylphosphino)ethane) are reduced by KC8 to afford the dimeric Ni(I) complex [(dtbpe)NiCl](2) (1) in 73% yield. Reaction of 1 with [FeCp2][PF6] effects a one-electron oxidation to give the mixed-valent Ni(I,II) binuclear species [{(dtbpe)NiCl}(2)][PF6], [1][PF6], Complex 1 reacts with the radicals NO and TEMPO (2,2,6,6-tetramethyl-1-piperidine-N-oxyl) to give the diamagnetic Ni(0) nitrosyl (dtbpe)Ni(Cl)(NO) (2) and the Ni(II) complex (dtbpe)Ni(Cl)(O,N:eta(2)-TEMPO) (3). Reduction of the S-S bond of diphenyldisulfide by 1 results in formation of the Ni(II) arylthiolate complex (dtbpe)NiCl(SPh) (4). The radical anions NaOCPh2 and KN2Ph2 react cleanly with 1 to afford (dtbpe)Ni(eta(2)- OCPh2) (5) and (dtbpe)Ni(eta(2)-N2Ph2) (6). Phenylacetylide C-C bond coupling is effected by reaction of 1 with LiC-CPh to form [(dtbpe)Ni(C,C':eta(2)-CCPh)](2) (7). In addition to standard spectroscopic (IR, NMR, EPR) and magnetic measurements, complexes 1, [1][PF6], 3, and 5 were also characterized by single-crystal X-ray diffraction methods. (C) 2002 Elsevier Science B.V. All rights reserved.

  DOI：

  10.1016/s0020-1693(02)01302-6

文献信息

• Monomeric Phosphido and Phosphinidene Complexes of Nickel
  作者：Rory Melenkivitz、Daniel J. Mindiola、Gregory L. Hillhouse

  DOI：10.1021/ja017787t

  日期：2002.4.1

  An unusual family of three-coordinate, d(8) and d(9) nickel phosphido and phosphinidene complexes containing the chelating 1,2-bis(di-tert-butylphosphino)ethane (dtbpe) ligand and a terminal PR(2)(-) or PR(2-) ligand have been prepared. The complexes (dtbpe)Ni[P(t-Bu)(2)] (2), [(dtbpe)Ni[=P(t-Bu)(2)](+)][PF(6)(-)] (3), [(dtbpe)Ni[=P(H)(dmp)](+)][PF(6)(-)] (5), and (dtbpe)Ni[=P(dmp)] (6) have been structurally

  包含螯合 1,2-双（二叔丁基膦）乙烷 (dtbpe) 配体和末端 PR(2)（ -) 或 PR(2-) 配体已经制备。配合物 (dtbpe)Ni[P(t-Bu)(2)] (2), [(dtbpe)Ni[=P(t-Bu)(2)](+)][PF(6)(-) ] (3), [(dtbpe)Ni[=P(H)(dmp)](+)][PF(6)(-)] (5), 和 (dtbpe)Ni[=P(dmp)] ( 6) 已通过单晶 X 射线衍射方法进行结构表征。三配位 d(8) 配合物表现出 Ni-P 键长和配体几何形状，表明它们参与了对称允许的配体与金属 pi 键合，涉及磷 p 电子和位于Ni协调平面。化合物 6 是后过渡金属末端膦叉化合物的罕见例子。
• A two-coordinate Ni(<scp>i</scp>) silyl complex: CO₂ insertion and oxidatively-induced silyl migrations
  作者：Ryan J. Witzke、T. Don Tilley

  DOI：10.1039/c9cc03128f

  日期：——

  reactivity of the first open-shell two-coordinate silyl complex, (IPr)Ni–Si(SiMe3)3, (IPr = 1,3-di(2,6-di-iso-propylphenyl)imidazolin-2-ylidene) is reported. Reaction with CO2 results in a novel insertion product that possesses a distorted geometry. Oxidations of the Ni center, with [Cp2Fe][B(C6F5)4] and Ph3CCl, result in migratory rearrangements of the silyl ligand, apparently via related silylene intermediates

  第一个开壳双配位甲硅烷基络合物（IPr）Ni-Si（SiMe 3）3（IPr = 1,3-二（2,6-二异丙基苯基）咪唑啉-2 -亚烷基）被报道。与CO 2的反应产生了一种新的插入产物，该插入产物具有扭曲的几何形状。用[Cp 2 Fe] [B（C 6 F 5）4 ]和Ph 3 CCl氧化Ni中心，显然会通过相关的甲硅烷基中间体导致甲硅烷基配体的迁移重排。不同的氧化产物通过引入或除去氯化物的反应相互转化。
• Synthesis and characterization of side-bound aryldiazo and end-bound nitrosyl complexes of nickel
  作者：Vlad M. Iluc、Alexander J. M. Miller、Gregory L. Hillhouse

  DOI：10.1039/b510131j

  日期：——

  Structural characterization of a nickel aryldiazo complex supported by the bulky 1,2-bis(di-tert-butylphosphino)ethane ligand reveals square-planar Ni geometry and an unusual side-on coordination mode for the N2R moiety, while the related nitrosyl complex displays trigonal-planar geometry at Ni and end-on coordination of the NO ligand.

  庞大的1,2-双（二叔丁基膦基）乙烷配体支撑的镍芳基重氮配合物的结构表征显示了方形的Ni几何形状和N2R部分的不寻常的侧面配位模式，而相关的亚硝酰基配合物则显示出来Ni的三角形平面几何形状和NO配体的末端配位。
• Hydrogen-Atom Abstraction from Ni(I) Phosphido and Amido Complexes Gives Phosphinidene and Imide Ligands
  作者：Vlad M. Iluc、Gregory L. Hillhouse

  DOI：10.1021/ja107115q

  日期：2010.11.3

  Hydrogen-atom abstraction from M-E(H) to generate M═E-containing complexes (E = PR, NR) is not well studied because only a few complexes are known to undergo such reactions. Hydrogen-atom abstraction from nickel(I) phosphide and amide complexes led to the corresponding phosphinidene and imide compounds. These reactions are unparalleled in the organometallic chemistry of nickel and feature an unusual

  从 ME(H) 提取氢原子以生成含 M=E 的配合物（E = PR，NR）尚未得到很好的研究，因为已知只有少数配合物会发生此类反应。从磷化镍 (I) 和酰胺络合物中提取氢原子产生相应的膦亚胺和酰亚胺化合物。这些反应在镍的有机金属化学中是无与伦比的，并且是通过氢原子提取合成的过渡金属膦的一个不寻常例子。
• Terminal Amido and Imido Complexes of Three-Coordinate Nickel
  作者：Daniel J. Mindiola、Gregory L. Hillhouse

  DOI：10.1021/ja010358a

  日期：2001.5.1