[Ni(1,2-bis(di-tert-butylphosphino)ethane)(μ-H)]2 | 220135-23-9

• 分子结构分类: 有机化合物 - 有机杂环化合物
• 英文名称: [Ni(1,2-bis(di-tert-butylphosphino)ethane)(μ-H)]2
• 英文别名: (((CH3)3C)2PC2H4P(C(CH3)3)2Ni)2(.mu-H.)2；[(1,2-bis(di-tert-butylphosphino)ethane)Ni(μ-H)]2；[nickel(1,2-bis-(di-tert-butylphosphino)ethane)H]2；[(dtbpe)NiH]2；[Ni(dtbpe)H]2
• CAS: 220135-23-9
• 化学式: C₃₆H₈₂Ni₂P₄
• 分子量: 756.322
• InChiKey: DXQCMGUDWPVXQX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  13.75
• 重原子数：
  42.0
• 可旋转键数：
  0.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  1.0
• 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：

  [Ni(1,2-bis(di-tert-butylphosphino)ethane)(μ-H)]2 以 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 在 activated Mg 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 生成 [Ni(1,2-bis(di-tert-butylphosphino)ethane)(μ-H)]2
  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

• Stereoselective Hydrogenation of Aromatic Alkynes Using Water, Triethylsilane, or Methanol, Mediated and Catalyzed by Ni(0) Complexes
  作者：Rigoberto Barrios-Francisco、Juventino J. García

  DOI：10.1021/ic801823x

  日期：2009.1.5

  inoethane or 1,2-bis(diterbutylphosphino-ethane) in the presence of water, triethylsilane/water, or methanol as hydrogen sources yields the selective production of E- or Z- aromatic alkenes from the corresponding alkynes. For instance, in the case of diphenylacetylene (dpa) and water, a metal-mediated process was found to yield trans-stilbene stoichiometrically, whereas in the case of triethylsilane/water

  使用该类型的复合物的[（PP）的Ni（η 2 - ç，Ç -alkyne）]（PP = 1,2-双（二-异丙基-膦基或1,2-双（diterbutylphosphino乙烷）在存在水，三乙基硅烷/水或甲醇作为氢源时，可以从相应的炔烃中选择性生产E-或Z-芳烃，例如，在二苯乙炔（dpa）和水的情况下，金属介导的过程为可以发现化学计量产生反式二苯乙烯，而在三乙基硅烷/水和甲醇的情况下，发现了催化体系（1％mol），催化体系转化为顺式或反式的比例> 95％。二苯乙烯，分别。还评估了芳环上各种取代基的使用。使用D 2 O进行氘标记的研究可以确认水是炔烃还原的氢源。
• Nickel Complexes Involved in the Isomerization of 2-Methyl-3-butenenitrile
  作者：Alberto Acosta-Ramírez、Areli Flores-Gaspar、Miguel Muñoz-Hernández、Alma Arévalo、William D. Jones、Juventino J. García

  DOI：10.1021/om061037g

  日期：2007.3.1

  The nickel(0) fragment [(P-P)Ni], where (P-P) = dcype (1,2-bis(dicyclohexylphosphino)ethane) or dtbpe (1,2-bis(di-tert-butylphosphino)ethane), reacts with the cyano-olefins involved in the isomerization process of 2-methyl-3-butenenitrile (2M3BN), producing the corresponding complex [(P-P)Ni(eta(2)-C,C-cyano-olefin)]. In the case of 2M3BN and 3-pentenenitrile (3PN), the pi-methylallyl metal complex was observed in solution. All of the intermediates in the catalytic cycle were detected and characterized by heteronuclear NMR spectroscopy; some of these were also characterized by single-crystal X-ray diffraction studies. The initial catalytic behavior of this system for the isomerization of 2M3BN was studied also.
• Nickel-Catalyzed Reductive Hydroesterification of Styrenes Using CO₂ and MeOH
  作者：Lucero González-Sebastián、Marcos Flores-Alamo、Juventino J. García

  DOI：10.1021/om300819d

  日期：2012.12.10

  Complexes [(dippe)Ni(mu-H)](2) (A) (dippe = 1,2-bis-di-isopropylphosphino)ethane) and [(dtbpe)Ni(mu-H)](2) (B) (dtbpe = 1,2-bis-di-tert-butylphospino)ethane) catalyze the reductive hydroesterification of styrenes with the use of CO2 and MeOH. The latter acts as a hydrogen source and as an esterificating agent, to yield the corresponding branched and linear esters in moderate to good yields. In all of the studied reactions the linear esters were obtained in higher amounts than the branched ones. When the hydroesterification reaction was carried out using a stoichiometric metal/substrate ratio, the complexes [(P-P)Ni(CO)(2)] and [(P-P)Ni(CO3)] (P-P = dippe or dtbpe) were isolated and characterized by standard spectroscopic methods. Compounds [(dtbpe)Ni(CO)(2)] and [(dtbpe)Ni(CO3)] were also fully characterized by single-crystal X-ray diffraction.
• σ-Borane Coordinated to Nickel(0) and Some Related Nickel(II) Trihydride Complexes
  作者：Marco G. Crestani、Miguel Muñoz-Hernández、Alma Arévalo、Alberto Acosta-Ramírez、Juventino J. García

  DOI：10.1021/ja056000m

  日期：2005.12.1

  The reactions of the complexes [(dcype)NiH](2), 1, [(dippe)NiH](2), 2, and [(dtbpe)NiH](2), 3, with a mixture of BEt3 and Super-Hydride (LiHBEt3) afforded sigma-borane nickel(O) compounds of the type [(dcype)Ni(sigma-HBEt2)], 4, [(dippe)Ni(sigma-HBEt2)], 5, [(dtbpe)Ni(sigma-HBEt2)], 6, respectively, with the concomitant formation in each case of [(dcype)(2)Ni-2(H)(3)][BEt4], 7, [(dippe)(2)Ni-2(H)(3)][BEt4], 8 and [(dtbpe)(2)Ni-2(H)(3)][BEt4], 9, respectively. X-ray crystal structures are reported for 4 and 8. The reaction of BEt3 and LiHBEt3 was also reviewed in detail.
• Formation of Phosphirenes by Phosphinidene Group-Transfer Reactions from (dtbpe)NiP(dmp) to Alkynes
  作者：Rory Waterman、Gregory L. Hillhouse

  DOI：10.1021/om0341754

  日期：2003.12.1