(bis(di-tert-butylphosphino)ethane)(η2-ethyne)nickel(0) | 150591-39-2

• 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: (bis(di-tert-butylphosphino)ethane)(η2-ethyne)nickel(0)
• 英文别名: (dtbpe)Ni(ethylene) complex；[Ni(C₂H₄)(1,2-bis(di-tertbutylphosphino)ethane)]；[Ni(C₂H₄)(dtbpe)]
• CAS: 150591-39-2
• 化学式: C₂₀H₄₂NiP₂
• 分子量: 403.191
• InChiKey: RVCJSMFSTLOPES-UHFFFAOYSA-N

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：

  (bis(di-tert-butylphosphino)ethane)(η2-ethyne)nickel(0) 、 1-isopropyl-3,4,5-triphenyl-1,2-diphosphacyclopenta-2,4-diene 以 氘代甲苯 为溶剂， 生成 (1-isopropyl-3,4,5-triphenyl-1,2-diphosphacyclopenta-2,4-diene)[1,2-bis(di-tert-butylphosphino)ethane]nickel
  参考文献：
  名称：

  基于 1-烷基-1,2-二磷的镍配合物的核磁共振研究

  摘要：

  使用 1D/2D 同相关和异相关 NMR 实验确定溶液中基于 1-烷基-1,2-二磷的镍配合物的结构。在配合物中观察到 P-P 键的 η2 配位模式。

  DOI：

  10.1007/s11172-019-2395-5
• 作为产物：
  描述：

  以 四氢呋喃 、 氘代四氢呋喃 为溶剂， 生成 (bis(di-tert-butylphosphino)ethane)(η2-ethyne)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

文献信息

• Preparation of a,B-Ethylenically Unsaturated Carboxylic Salts By Catalytic Carboxylation Of Alkenes
  申请人：BASF SE

  公开号：US20130172616A1

  公开（公告）日：2013-07-04

  In a process for preparing an alkali metal or alkaline earth metal salt of an α,β-ethylenically unsaturated carboxylic acid, a) a transition metal-alkene complex is reacted with CO 2 to give a metallalactone, b) the metallalactone is reacted with a base to give an adduct of the alkali metal or alkaline earth metal salt of the α,β-ethylenically unsaturated carboxylic acid with the transition metal complex, and c) the adduct is reacted with an alkene to release the alkali metal or alkaline earth metal salt of the α,β-ethylenically unsaturated carboxylic acid and regenerate the transition metal-alkene complex. The base is selected from alkali metal or alkaline earth metal hydroxides and alkali metal or alkaline earth metal superbases. The alkene is, for example, ethene. The transition metal complex comprises, for example, nickel and a bidentate P,P, P,N, P,O or P,carbene ligand, such as 1,2-bis(di-tert-butylphosphino)ethane.

  在制备α，β-乙烯基不饱和羧酸的碱金属或碱土金属盐的过程中，a) 过渡金属-烯烃配合物与CO2反应形成金属内酯，b) 金属内酯与碱反应形成α，β-乙烯基不饱和羧酸的碱金属或碱土金属盐与过渡金属配合物的加合物，c) 加合物与烯烃反应释放出α，β-乙烯基不饱和羧酸的碱金属或碱土金属盐，并再生过渡金属-烯烃配合物。碱为选自碱金属或碱土金属的氢氧化物和碱金属或碱土金属的超碱。烯烃可以是乙烯等。过渡金属配合物包括镍和双齿P，P，P，N，P，O或P，卡宾配体，例如1,2-双(二叔丁基膦基)乙烷。
• Poerschke, Klaus-Richard; Pluta, Christian; Proft, Bernd, Zeitschrift fur Naturforschung, B: Chemical Sciences, 1993, vol. 48, # 5, p. 608 - 626
  作者：Poerschke, Klaus-Richard、Pluta, Christian、Proft, Bernd、Lutz, Frank、Krueger, Carl

  DOI：——

  日期：——
• Synthesis, Structure, and Reactivity of (^tBu₂PC₂H₄P^tBu₂)Ni(CH₃)₂ and {(^tBu₂PC₂H₄P^tBu₂)Ni}₂(μ-H)₂
  作者：Ingrid Bach、Richard Goddard、Carsten Kopiske、Klaus Seevogel、Klaus-Richard Pörschke

  DOI：10.1021/om980705y

  日期：1999.1.1

  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.
• NMR study of the Ni complexes based on 1-alkyl-1,2-diphospholes
  作者：S. A. Kondrashova、Yu. S. Ganushevich、S. V. Kharlamov、V. A. Milyukov、Sh. K. Latypov

  DOI：10.1007/s11172-019-2395-5

  日期：2019.2

  The structures of the nickel complexes based on 1-alkyl-1,2-diphospholes in a solution were determined using 1D/2D homo- and heterocorrelation NMR experiments. The η2 coordination mode at the P–P bond is observed in the complexes.

  使用 1D/2D 同相关和异相关 NMR 实验确定溶液中基于 1-烷基-1,2-二磷的镍配合物的结构。在配合物中观察到 P-P 键的 η2 配位模式。