[(1,2-bis(di-tert-butylphosphino)ethane)Ni]2(μ-η²:η²-C₆H₆) | 182817-76-1

• 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: [(1,2-bis(di-tert-butylphosphino)ethane)Ni]2(μ-η²:η²-C₆H₆)
• 英文别名: [(dtbpe)Ni]2(μ-η²:η²-C₆H₆)；[((1,2-bis(di-tert-butylphosphino)ethane)Ni)2(η2,μ-C6H6)]；benzene;ditert-butyl(2-ditert-butylphosphanylethyl)phosphane;nickel
• CAS: 182817-76-1
• 化学式: C₄₂H₈₆Ni₂P₄
• 分子量: 832.42
• InChiKey: YSPHJHZOJXLQGZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
  None
• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  [(1,2-bis(di-tert-butylphosphino)ethane)Ni]2(μ-η²:η²-C₆H₆) 以 not given 为溶剂， 生成 (bis(di-tert-butylphosphino)ethane)(η2-ethene)nickel(0)
  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：

  carbanide;ditert-butyl(2-ditert-butylphosphanylethyl)phosphane;nickel(2+) 、 苯 以 苯 为溶剂， 以59%的产率得到[(1,2-bis(di-tert-butylphosphino)ethane)Ni]2(μ-η²:η²-C₆H₆)
  参考文献：
  名称：

  Synthesis, Structure, and Properties of {(^tBu₂PC₂H₄P^tBu₂)Ni}₂(μ-η²:η²-C₆H₆) and (^tBu₂PC₂H₄P^tBu₂)Ni(η²-C₆F₆)¹

  摘要：

  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.

  DOI：

  10.1021/om960389s
• 作为试剂：
  描述：

  3-苯基-2-甲苯磺酰-1,2-氧杂氮杂环丙烷 在 [(1,2-bis(di-tert-butylphosphino)ethane)Ni]2(μ-η²:η²-C₆H₆) 作用下， 以 四氢呋喃 为溶剂， 反应 1.0h， 生成 N-苯甲酰基-4-甲基-苯磺酰胺
  参考文献：
  名称：

  用低价镍配合物裂解奥氮丙啶：竞争性地从氧杂氮杂（II）环丁烷中裂解出O和CN片段

  摘要：

  反应低价镍配合物[（dtbpe）的Ni] 2（μ-η 2：η 2 -C 6 H ^ 6）与氧氮环丙烷被发现的亚胺，酰胺和醛产物形式的混合物。如果恶唑烷的N-取代基足够大，则可以分离短寿命的中间体，并通过X射线衍射研究表征为恶二氮杂（II）环丁烷。这是第一个明确定义的示例，是将氧氮丙啶N-O氧化加成到过渡金属上。此恶杂氮杂镍环丁烷的后续裂解形成包括镍在内的复杂的产物混合物（II）亚氨基络合物，表明恶唑烷可作为亚硝基前体。初步分析机制与oxazanickelacyclobutane碎裂的双金属机制，以形成镍酰亚胺和η一致2 -醛络合物。

  DOI：

  10.1039/c7cc07690h

文献信息

• Synthesis and structure of a terminal dinitrogen complex of nickel
  作者：Rory Waterman、Gregory L Hillhouse

  DOI：10.1139/v05-011

  日期：2005.4.1

  Reaction of petroleum ether solutions of [(dtbpe)Ni]₂(η²,µ-C₆H₆) (1, dtbpe = 1,2-bis(di-tert-butylphosphino)ethane) with triphenylphosphine under a dinitrogen atmosphere gives the Ni(0) dinitrogen adduct (dtbpe)Ni(N₂)(PPh₃) (2), which can be isolated as dark red crystals in 87% yield. The X-ray crystal structure of 2 reveals pseudotetrahedral geometry about Ni and a terminal dinitrogen ligand with Ni—N(1) = 1.830(2) Å, N(1)—N(2) = 1.112(2) Å, and Ni-N(1)-N(2) = 177.5(2)°. Key words: dinitrogen, nickel, X-ray.

  在二氮化物气氛下，石油醚溶液中的[(dtbpe)Ni]2(η2,µ-C6H6)（1，dtbpe = 1,2-双叔丁基膦乙烷）与三苯基膦反应，生成Ni（0）二氮化物加合物（dtbpe）Ni（N2）（PPh3）（2），可以以87％的收率分离为深红色晶体。 2的X射线晶体结构显示Ni周围的假四面体几何结构和具有Ni-N（1）= 1.830（2）Å，N（1）-N（2）= 1.112（2）Å和Ni-N（1）-N（2）= 177.5（2）°的末端二氮化物配体。关键词：二氮化物，镍，X射线。
• Three-Coordinate Nickel Carbene Complexes and Their One-Electron Oxidation Products
  作者：Vlad M. Iluc、Gregory L. Hillhouse

  DOI：10.1021/ja501900j

  日期：2014.4.30

  The synthesis and characterization of two new carbene complexes, (dtbpe)Ni═CH(dmp) (1; dtbpe = 1,2-bis(di-tert-butylphosphino)ethane; dmp = 2,6-dimesitylphenyl) and (dippn)Ni═CH(dmp) (2; dippn = 1,8-bis(di-iso-propylphosphino)naphthalene), are described. Complexes 1 and 2 were isolated by photolysis of the corresponding side-bound diazoalkane complexes, exemplified by (dtbpe)Niη(2)-N2CH(dmp)} (3)

  两种新卡宾配合物 (dtbpe)Ni=CH(dmp) (1; dtbpe = 1,2-双(二叔丁基膦) 乙烷; dmp = 2,6-二甲苯基苯基) 和 (dippn) 的合成和表征描述了 Ni=CH(dmp) (2；dippn = 1,8-双(二-异丙基膦基)萘)。配合物 1 和 2 通过光解相应的侧结合重氮烷配合物分离，例如 (dtbpe)Niη(2)-N2CH(dmp)} (3)。卡宾配合物具有较短的 Ni-C 距离和介于 120° 和 180°（分别为 155.7(3)° 和 152.3(3)°）之间的卡宾碳的 Ni-CC 角。当研究它们对 1 电子氧化剂的反应性时，两种卡宾之间的差异变得明显：1 的氧化导致内部重排并形成镍 (I) 烷基 [κ(2)-P, C-二叔丁基膦基-二叔丁基-PCH(dmp)乙烷}Ni][BAr(F)4] (4)，而 2 的氧化允许分离未重排的产物，配制