Ni(CO)2(2,2'-bipyridine) | 14917-14-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: Ni(CO)2(2,2'-bipyridine)
• 英文别名: (2,2′ -bipyridyl)Ni(CO)₂；(2,2′ -bpy)Ni(CO)₂；nickel(0)(2,2'-bipyridine)(CO)2；Ni(2,2'-bipyridyl)(carbon monoxide)2；carbon monoxide;nickel;2-pyridin-2-ylpyridine
• CAS: 14917-14-7
• 化学式: C₁₂H₈N₂NiO₂
• 分子量: 270.898
• InChiKey: HAWCFUXSERZQBD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
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• 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：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为反应物：
  描述：

  Ni(CO)2(2,2'-bipyridine) 在 CO 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 生成 tetracarbonyl nickel
  参考文献：
  名称：

  Garnier, L.; Rollin, Y.; Perichon, J., New Journal of Chemistry, 1989, vol. 13, p. 53 - 60

  摘要：

  DOI：
• 作为产物：
  描述：

  diethyl(2,2'-bipyridyl)nickel(II) 以 四氢呋喃 为溶剂， 生成 Ni(CO)2(2,2'-bipyridine)
  参考文献：
  名称：

  Nickel-Mediated Formation of Thio Esters from Bound Methyl, Thiols, and Carbon Monoxide: A Possible Reaction Pathway of Acetyl-Coenzyme A Synthase Activity in Nickel-Containing Carbon Monoxide Dehydrogenases

  摘要：

  Current mechanistic proposals for the acetyl synthase activity of nickel-containing carbon monoxide dehydrogenases (CH3-THF + CoA . SH --> CoA . SCOCH3 + THF; THF = tetrahydrofolate, CoA . SH = coenzyme A) implicate a Ni catalytic center and the steps [Ni-CH3] --> [Ni-COCH3] --> CoA . SCOCH3. The second step presumably involves attack by the sulfur nucleophile of coenzyme A at the acyl carbon atom in the overall reaction [Ni-II-COCH3] + RS(H) --> RSCOCH(3) + Ni-II (+ H+) + 2e(-). We have previously demonstrated these steps in Ni(II) complexes with physiological-type ligation. In this work, it is shown that the reaction of acyl and thiolate ligands coordinated to Ni(II) affords thioesters in high yield, The complex [Ni(bpy)(CH3)(2)], established to be planar by an X-ray structure determination, reacts with 1 equiv of arenethiol to afford diamagnetic planar [Ni(bpy)(CH3)(SR)] (8) with R = p-C6H4CH3, 2,6-C6H3(CH3)2 (8b), mesityl (8c), 2,4,6-C(6)H(2)iPr(3), and 2,6-C6H3Cl2 (8e) (bpy = 2,2'-bipyridyl). An analogous reaction gives [Ni(bpy)(C2H5)(S-mesityl)] (12) from [Ni(bpy)(C2H5)(2)]. Planar structures of 8c,e were confirmed by X-ray analysis. Complexes 12 and 8 with different R substituents undergo thiolate ligand exchange in THF with K-eq approximate to 1. Reaction of 8e with 1 equiv of carbon monoxide yields the acyl complex [Ni(bpy)(COCH3)(S-2,6-C6H3Cl2)] (9a), whose planar coordination unit was confirmed by X-ray methods. Treatment of the complexes 8 in THF with more than 3 equiv of carbon monoxide yields [Ni(bpy)(CO)(2)] and the thioesters RSCOCH(3) in 96-100% yield in situ. A solution initially containing 8b and 12 gave under the same conditions four thioesters in equal amounts, consistent with four complexes in the equilibrated solution prior to reaction with carbon monoxide. Reaction of 9a in THF with carbon monoxide produced 2,6-dichlorophenyl thioacetate quantitatively, indicating that Ni(II)-acyl-thiolate complexes are intermediates in thioester formation. The overall reaction is [Ni(bpy)(R')(SR)] + 3CO --> RSCOR' + [Ni(bpy)(CO)2] (R' = CH3, C2H5); the two electrons in the generalized reaction are captured by the metal as Ni(0). A related and necessarily intramolecular reaction of [Ni(bpy)(SCH2CH2CH2)] was confirmed and shown to produce gamma-thiobutyrolactone in quantitative yield in situ. Evidence supporting an analogous intramolecular path for reaction systems based on 8 is summarized. This investigation provides the first examples of Ni-mediated acyclic thioester synthesis and demonstrates a possible means of enzymatic thioester formation should coenzyme A(-) and an acetyl group coordinate to the Ni(II) catalytic center.

  DOI：

  10.1021/ja00129a011
• 作为试剂：
  描述：

  二氧化碳 、 对溴三氟甲苯 在 Ni(CO)2(2,2'-bipyridine) 四丁基溴化铵 作用下， 以 various solvent(s) 为溶剂， 以10%的产率得到1-(三氟甲基)-4-[4-(三氟甲基)苯基]苯
  参考文献：
  名称：

  2,2'-联吡啶-镍配合物催化有机卤化物和二氧化碳电催化合成对称酮

  摘要：

  在二氧化碳在N-甲基吡咯烷酮或二甲基甲酰胺作为溶剂的存在下，对2,2'-联吡啶-镍配合物进行电化学还原，得到了与两个CO分子相关的相应的镍（0）配合物。烷基卤化物的氧化加成到此配合物上，然后发生内部CO转移和还原消除，导致与镍（II）一起以高收率形成对称的酮，而芳基或乙烯基卤化物则主要生成酰基衍生物。镍（0）物种进行了电化学再生，因此产生了有效的催化过程。讨论了这些反应的可能机理。

  DOI：

  10.1016/0022-328x(89)87056-1

文献信息

• Preparation of Ni- or Pt-Containing Cyclic Esters by Oxidative Addition of Cyclic Carboxylic Anhydrides and Their Properties
  作者：Kenji Sano、Takakazu Yamamoto、Akio Yamamoto

  DOI：10.1246/bcsj.57.2741

  日期：1984.10

  Metal containing cyclic ester complexes, (Remark: Graphics omitted.)(L=1,2-bis(diphenylphosphino)ethane (dpe) or 2,2′-bipyridine (bpy); R1, R2=H or CH3) and (Remark: Graphics omitted.) (L=tricyclohexylphosphine (PCy3) or dpe; n=1 or 2), have been prepared by oxidative addition of cyclic carboxylic anhydrides to zero-valent metal complexes. These complexes have been characterized by elemental analysis

  含金属环酯络合物，（备注：图示省略。）（L=1,2-双（二苯基膦基）乙烷（dpe）或2,2'-联吡啶（bpy）；R1、R2=H或CH3）和（备注：图形省略。）（L=三环己基膦（PCy3）或dpe；n=1或2），是通过将环状羧酸酐氧化加成到零价金属络合物来制备的。这些配合物已通过元素分析和光谱学（IR 以及 1H-、13C1H}-和 31P1H}-NMR）和化学反应性进行表征。琥珀酸酐氧化加成到 Ni(bpy)(cod)（cod=1,5-环辛二烯）的速率由二阶速率方程表示，R=k[Ni(bpy)(cod)][琥珀酸酐]和 k 的温度依赖性给出了 68 kJ mol-1 的活化能。
• Insertion of Carbon Monoxide into Nickel-Alkyl Bonds of Monoalkyl-and Dialkylnickel(II) Complexes, NiR(Y)L₂and NiR₂L₂. Preparation of Ni(COR)(Y)L₂from NiR(Y)L₂and Selective Formation of Ketone, Diketone, and Aldehyde from NiR₂L₂
  作者：Takakazu Yamamoto、Teiji Kohara、Akio Yamamoto

  DOI：10.1246/bcsj.54.2161

  日期：1981.7

  Reactions of monoalkylnickel(II) complexes, NiR(Y)L2 (R=CH3, C2H5; Y=Cl, suc(succinimido), pht(phthalimido), OC6H4-p-CN; L=1/2 bpy (2,2′-bipyridine), PEt3 (triethylphosphine)), with CO afford monoacylnickel(II) complexes, Ni(COR)(Y)L2, which are characterized by elemental analysis and spectroscopies (IR and NMR). Reactions of the acylnickel(II) complexes with alcohols and aniline give the corresponding esters and amides, respectively. Exposure of Ni(COR)(Y)L2 to dry air leads to oxidation of RCO to a RCOO ligand giving a complex formulated as Ni(OCOR)(Y)L2. Reactions of dimethylnickel(II) complexes, Ni(CH3)2L2 (L=1/2 bpy, PEt3, 1/2 dpe (1,2-bis(diphenylphosphino)ethane, 1/2 dpp (1,3-bis(diphenylphosphino)propane), with carbon monoxide afford acetone and/or 2,3-butanedione in medium to high yields, the acetone/2,3-butanedione ratio varying with the ligand L, reaction temperature, and additives such as maleic anhydride and triphenylphosphine. Generally the acetone/2,3-butanedione ratio decreases with increase in thermal stabilities of Ni(CH3)2L2. Ni(C2H5)2(bpy) and Ni(n-C3H7)2(bpy) give 3-pentanone and 4-heptanone, respectively, on treating them with CO, whereas Ni(C2H5)2(dpe) produces C2H5CHO and C2H4.

  甲基或乙基镍(II)配合物NiR(Y)L2 (R=CH3, C2H5; Y=Cl, succ(琥珀酰亚胺), pht(酞酰亚胺), OC6H4-p-CN; L=1/2 bpy (2,2'-联吡啶), PEt3 (三乙基膦))与CO反应生成单酰基镍(II)配合物Ni(COR)(Y)L2, 该化合物通过元素分析和光谱学(IR和NMR)进行表征。酰基镍(II)配合物与醇和苯胺反应生成相应的酯和酰胺。将Ni(COR)(Y)L2暴露于干燥空气中会导致RCO氧化成RCOO配体, 生成化学式为Ni(OCOR)(Y)L2的配合物。二甲基镍(II)配合物Ni( )2L2 (L=1/2 bpy, PEt3, 1/2 dpe (1,2-双(二苯基膦)乙烷), 1/2 dpp (1,3-双(二苯基膦)丙烷))与一氧化碳反应生成中等至高产率丙酮和/或2,3-丁二酮, 丙酮/2,3-丁二酮的比例随配体L、反应温度和马来酸酐及三苯基膦等添加剂的不同而变化。通常, 随着Ni( )2L2热稳定性的增加, 丙酮/2,3-丁二酮的比例下降。Ni( )2(bpy)和Ni(n-C3H7)2(bpy)用CO处理分别生成3-戊酮和4-庚酮, 而Ni( )2(dpe)生成 CHO和C2H4.
• Electrochemical generation of a nickel–carbonyl complex, catalyst for the electroreductive coupling of organic halides and carbon monoxide into ketones
  作者：M. Oçafrain、M. Devaud、J.Y. Nédelec、M. Troupel

  DOI：10.1016/s0022-328x(98)00515-4

  日期：1998.6

  electroreductive coupling of organic halides and carbon monoxide into ketones. The active species is obtained from a stoichiometric mixture of Ni0, 2,2′-bipyridine and CO. The electrochemical method used to generate this complex allows a good tuning of Ni0 production versus CO dissolution. We have shown that Ni(CO)bpy results from a CO equilibrium exchange between Ni(CO)2bpy and Nibpy.

  镍-羰基配合物Ni（CO）bpy参与了有机卤化物和一氧化碳在镍催化下的酮的电子催化还原反应。的活性种选自Ni的化学计量混合物得到0，2,2'-联吡啶和CO。用于生成这种复杂的电化学方法允许Ni的良好调谐0生产与CO溶解。我们已经表明，Ni（CO）bpy是由Ni（CO）2 bpy和Nibpy之间的CO平衡交换产生的。
• Nickel–bipyridine catalysed electrosynthesis of ketones from organic halides and carbon monoxide: kinetic and mechanistic investigations
  作者：M. Oçafrain、E. Dolhem、J.Y. Nedelec、M. Troupel

  DOI：10.1016/s0022-328x(98)00851-1

  日期：1998.11

  The reactivity of zerovalent nickel-2,2′-bipyridine complexes towards carbon monoxide and organic halides was investigated by electroanalytical methods. The kinetic data obtained allow us to propose two pathways leading to the formation of an acylnickel complex by electroreduction of Nibpy2+ in the presence of both CO and a halocarbon.

  通过电分析方法研究了零价镍2,2'-联吡啶配合物对一氧化碳和有机卤化物的反应性。所获得的动力学数据使我们能够提出两种途径，通过在CO和卤代烃的存在下通过Nibpy 2+的电还原来形成酰基镍配合物。
• Gmelin Handbuch der Anorganischen Chemie, Gmelin Handbook: Ni: Org.Verb.2, 2.1.4.5, page 262 - 266
  作者：

  DOI：——

  日期：——