(dtbpe)NiCl2 | 138549-52-7

• 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)NiCl2
• 英文别名: dichloro(1,2-bis(di-tert-butylphosphino)ethane)nickel(II)；ditert-butyl(2-ditert-butylphosphanylethyl)phosphane;dichloronickel
• CAS: 138549-52-7
• 化学式: C₁₈H₄₀Cl₂NiP₂
• 分子量: 448.059
• InChiKey: YSKMPPLXVPGBIW-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  8.52
• 重原子数：
  23
• 可旋转键数：
  7
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  (dtbpe)NiCl2 在 activated Mg 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 生成
  参考文献：
  名称：

  Synthesis, Structure, and Reactivity of (^tBu₂PC₂H₄P^tBu₂)Ni(CH₃)₂ and {(^tBu₂PC₂H₄P^tBu₂)Ni}₂(μ-H)₂

  摘要：

  Oxidative addition of CH3I to (d(t)bpe)Ni(C2H4) (d(t)bpe = (Bu2PC2H4PBu2)-Bu-t-Bu-t) affords (d(t)bpe)-Ni(I)CH3 (I). The reaction of (d(t)bpe)NiCl2 or 1 with the stoichiometric quantity of (tmeda)Mg(CH3), yields (d(t)bpe)Ni(CH3)(2) (2). (d(t)bpe)Ni(I)CD3 (1-d(3)) and (d(t)bpe)Ni(CD3)(2) (2-d(6)) have been prepared analogously. Thermolysis of 2 in benzene affords {(d(t)bpe)Ni}(2)(mu-eta(2):eta(2)-C6H6) (4). The reaction of either 2 or 4 with hydrogen (H-2, HD, D-2) gives {(d(t)bpe)Ni}(2)(mu-H)(2) (3) and the isotopomers {(d(t)bpe)Ni}(2)(mu-H)(mu-D) (3-d) and {(d(t)bpe)Ni}(2)(mu-D)(2) (3-d(2)). According to the NMR spectra, the structure of 3 is dynamic in solution. The crystal structures of 2 and 3 have been determined by X-ray crystallography, Solution thermolysis of 2 or reduction of (dtbpe)NiCl2 with Mg* in the presence of alkanes probably involves a-complex-type intermediates [(d(t)bpe)Ni(eta(2)-R'H)] (R' = e.g. C2H5, A). While the nonisolated [(d(t)bpe)Ni-0] a-complexes A are exceedingly reactive intermediates, isolated 3 and 4 represent easy to handle starting complexes for [(d(t)bpe)Ni-0] reactions. Partial protolysis of 2 with CF3SO3H affords (d(t)bpe)Ni(CH3)(OSO2CF3) (5). Complex 5 reacts slowly with 2 equiv of ethene to give equimolar amounts of [(d(t)bpe)Ni(C2H5)](+)(OSO2CF3-) (6) and propene. The reaction is thought to be initiated by an insertion of ethene into the Ni-CH3 bond of 5 to form the intermediate [(d(t)bpe)Ni(C3H7)(OSO2CF3)] (G), followed by elimination of propene to give the hydride intermediate [(d(t)bpe)Ni(H)(OSO2CF3)] (H), which on insertion of ethene into the Ni-H bond affords 6.

  DOI：

  10.1021/om980705y
• 作为产物：
  描述：

  1,2-双(二-叔丁基磷酰)乙烷 、 nickel dichloride 以 甲醇 为溶剂， 以78%的产率得到(dtbpe)NiCl2
  参考文献：
  名称：

  Synthesis, Structure, and Reactivity of (^tBu₂PC₂H₄P^tBu₂)Ni(CH₃)₂ and {(^tBu₂PC₂H₄P^tBu₂)Ni}₂(μ-H)₂

  摘要：

  Oxidative addition of CH3I to (d(t)bpe)Ni(C2H4) (d(t)bpe = (Bu2PC2H4PBu2)-Bu-t-Bu-t) affords (d(t)bpe)-Ni(I)CH3 (I). The reaction of (d(t)bpe)NiCl2 or 1 with the stoichiometric quantity of (tmeda)Mg(CH3), yields (d(t)bpe)Ni(CH3)(2) (2). (d(t)bpe)Ni(I)CD3 (1-d(3)) and (d(t)bpe)Ni(CD3)(2) (2-d(6)) have been prepared analogously. Thermolysis of 2 in benzene affords {(d(t)bpe)Ni}(2)(mu-eta(2):eta(2)-C6H6) (4). The reaction of either 2 or 4 with hydrogen (H-2, HD, D-2) gives {(d(t)bpe)Ni}(2)(mu-H)(2) (3) and the isotopomers {(d(t)bpe)Ni}(2)(mu-H)(mu-D) (3-d) and {(d(t)bpe)Ni}(2)(mu-D)(2) (3-d(2)). According to the NMR spectra, the structure of 3 is dynamic in solution. The crystal structures of 2 and 3 have been determined by X-ray crystallography, Solution thermolysis of 2 or reduction of (dtbpe)NiCl2 with Mg* in the presence of alkanes probably involves a-complex-type intermediates [(d(t)bpe)Ni(eta(2)-R'H)] (R' = e.g. C2H5, A). While the nonisolated [(d(t)bpe)Ni-0] a-complexes A are exceedingly reactive intermediates, isolated 3 and 4 represent easy to handle starting complexes for [(d(t)bpe)Ni-0] reactions. Partial protolysis of 2 with CF3SO3H affords (d(t)bpe)Ni(CH3)(OSO2CF3) (5). Complex 5 reacts slowly with 2 equiv of ethene to give equimolar amounts of [(d(t)bpe)Ni(C2H5)](+)(OSO2CF3-) (6) and propene. The reaction is thought to be initiated by an insertion of ethene into the Ni-CH3 bond of 5 to form the intermediate [(d(t)bpe)Ni(C3H7)(OSO2CF3)] (G), followed by elimination of propene to give the hydride intermediate [(d(t)bpe)Ni(H)(OSO2CF3)] (H), which on insertion of ethene into the Ni-H bond affords 6.

  DOI：

  10.1021/om980705y

文献信息

• Synthesis of 2-Nickela(II)oxetanes from Nickel(0) and Epoxides: Structure, Reactivity, and a New Mechanism of Formation
  作者：Addison N. Desnoyer、Eric G. Bowes、Brian O. Patrick、Jennifer A. Love

  DOI：10.1021/jacs.5b06735

  日期：2015.10.14

  frequently invoked as reactive intermediates in catalytic reactions of epoxides using nickel, but have never been isolated or experimentally observed in these transformations. Herein, we report the preparation of a series of well-defined nickelaoxetanes formed via the oxidative addition of nickel(0) with epoxides featuring ketones. The stereochemistry of the products is retained, which has not yet been reported

  2-镍氧杂环丁烷经常被用作使用镍的环氧化物催化反应中的反应中间体，但在这些转化中从未被分离或通过实验观察到。在此，我们报告了通过将镍 (0) 与具有酮的环氧化物氧化加成形成的一系列明确定义的镍氧杂环丁烷的制备。保留了产物的立体化学，尚未报道镍氧杂环丁烷。理论计算支持通过协同氧化加成的双金属开环/闭环途径。镍氧杂环丁烷的初始反应性研究表明，当用适当的试剂处理时，会发生质子分解、氧化诱导的还原消除、脱氧和消除反应。
• Investigations on the catalytic carboxylation of olefins with CO₂ towards α,β-unsaturated carboxylic acid salts: characterization of intermediates and ligands as well as substrate effects
  作者：Ivana Jevtovikj、Simone Manzini、Matthias Hanauer、Frank Rominger、Thomas Schaub

  DOI：10.1039/c5dt01040c

  日期：——

  salts and a detailed investigation on the critical steps in the catalysis are reported. The influence of two chelating phosphine ligands and several olefins on the elemental steps of the catalysis is shown. The work focusses on the formation of intermediate olefin complexes, lactone formation and base induced elimination of the lactone. The direct carboxylation of olefins is possible using nickel catalysts

  报道了乙烯以外的烯烃向α，β-不饱和羧酸盐的羧化以及对催化关键步骤的详细研究。显示了两种螯合膦配体和几种烯烃对催化元素步骤的影响。这项工作集中在中间烯烃配合物的形成，内酯的形成和碱引起的内酯的消除上。使用镍催化剂可以使烯烃直接羧化，这开辟了一条通往所需α，β-不饱和羧酸盐的新途径。该反应对1,3-二烯特别有效，并通过烯丙基羧酸盐的形成。在这种情况下，形成这种烯丙基型内酯复合物的能力似乎是向满意的营业额迈出的最具挑战性的一步。
• Exploring Regioselective Bond Cleavage and Cross-Coupling Reactions using a Low-Valent Nickel Complex
  作者：Addison N. Desnoyer、Florian W. Friese、Weiling Chiu、Marcus W. Drover、Brian O. Patrick、Jennifer A. Love

  DOI：10.1002/chem.201504959

  日期：2016.3.14

  systematic study of the reactivity of a series of esters and thioesters with [(dtbpe)Ni}2(μ‐η2:η2‐C6H6)] (dtbpe=1,2‐bis(di‐tert‐butyl)phosphinoethane), which is a source of (dtbpe)nickel(0). Trifluoromethylthioesters were found to form η2‐carbonyl complexes. In contrast, acetylthioesters underwent rapid Cacyl−S bond cleavage followed by decarbonylation to generate methylnickel complexes. This decarbonylation

  最近，酯作为交叉偶联反应的重金属化伙伴受到了广泛关注。在本文中，我们报道了一系列酯和硫酯的具有的反应性的系统研究[（dtbpe）的Ni} 2（μ-η 2：η 2 -C 6 H ^ 6）]（dtbpe = 1,2-双（二（叔丁基）膦乙烷乙烷），它是（dtbpe）镍（0）的来源。发现Trifluoromethylthioesters以形成η 2 -羰基络合物。相比之下，乙酰硫酯经历了快速的C酰基反应-S键裂解，然后脱羰以生成甲基镍络合物。该脱羰基可以通过添加CO而向后推动，从而使硫酯再生。发现大多数硫酯配合物与苯基硼酸发生化学计量交叉偶联，生成硫化物。虽然三氟乙酸乙酯还发现，形成η 2 -羰基络合物，苯基酯被发现主要经历Ç芳-O键裂解产生芳基镍络合物。这些也可以进行金属转移以产生联芳基。配体争夺产生双（乙酸）镍配合物阻碍了使反应具有催化性的尝试，其形成受到独立合成的支持。最后，乙酸2-萘酯也
• 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
  作者：Daniel J Mindiola、Rory Waterman、David M Jenkins、Gregory L Hillhouse

  DOI：10.1016/s0020-1693(02)01302-6

  日期：2003.3

  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.
• Synthesis, Structure, and Properties of {(^tBu₂PC₂H₄P^tBu₂)Ni}₂(μ-η²:η²-C₆H₆) and (^tBu₂PC₂H₄P^tBu₂)Ni(η²-C₆F₆)¹
  作者：Ingrid Bach、Klaus-Richard Pörschke、Richard Goddard、Carsten Kopiske、Carl Krüger、Anna Rufińska、Klaus Seevogel

  DOI：10.1021/om960389s

  日期：1996.11.12

  Thermolysis of ((t)Bu(2)PC(2)H(4)P(t)Bu(2))NiMe(2) in benzene or reduction of ((t)Bu(2)PC(2)H(4)P(t)Bu(2))NiCl2 with Mg* in THF/benzene affords a solution of mononuclear ((t)Bu(2)PC(2)H(4)P(t)Bu(2))Ni(eta(2)-C6H6) (1) and dinuclear ((t)Bu(2)PC(2)H(4)P(t)Bu(2))Ni}(2)(mu-eta(2):eta(2)-C6H6) (2) in equilibrium. Complex 2 has been isolated; the X-ray structure analysis reveals an antifacial coordination of the [((t)Bu(2)PC(2)H(4)P(t)Bu(2))Ni-0] moieties to adjacent C=C bonds of a formal cyclohexatriene ligand. According to solid-state and solution NMR the structure of 2 is static in the solid and fluxional in solution. Displacement of the benzene ligand in 1 or 2 by C6F6 affords mononuclear ((t)Bu(2)PC(2)H(4)P(t)Bu(2))Ni(eta(2)-C6F6) (5) for which the molecular structure is also reported.