diethyl(2,2'-bipyridyl)nickel(II) | 15218-76-5

• 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: diethyl(2,2'-bipyridyl)nickel(II)
• 英文别名: Ni(2,2'-bipyridine)Et2；diethyldipyridylnickel；Ni(bipy)Et₂；(2,2'-bipyridine)Ni(Et)₂；BipyNi(Et)₂；diethylnickel(2,2'-bipyridine)；diethylbipyridylnickel；Et2Ni(bipy)
• CAS: 15218-76-5
• 化学式: C₁₄H₁₈N₂Ni
• 分子量: 273.0
• InChiKey: BFRLMWCXGNRQPU-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：

  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
• 作为产物：
  描述：

  以 四氢呋喃 为溶剂， 生成 二甲基氧化锡 、 diethyl(2,2'-bipyridyl)nickel(II)
  参考文献：
  名称：

  Preparation and Properties of Monoalkylnickel(II) Complexes Having a Phenoxo, Benzenethiolato, Oximato, β-Diketonato, or Halo Ligand

  摘要：

  通过二烷基镍（II）配合物NiR\({}_2\)L\({}_2\)（1）与相应的活泼氢化合物HY的反应，制备了13种NiR（Y）Ln类型的配合物（R = CH\({}_3\)（Me），C\({}_2\)H\({}_5\)（Et）；Y = OC\({}_{6}\)H\({}_{5}\)，对氰基苯氧基，8-苯基苯氧基，8-喹啉氧基，OCOEt，OCOPh，苯乙酮肟基，乙酰丙酮基，苯甲酰丙酮基，Cl；L = 三乙基膦（PEt\({}_{3}\)），2，2′-联吡啶（bpy））。1与R′COY（Y = OC\({}_{6}\)H\({}_{5}\)，OCOC\({}_{6}\)H\({}_{5}\)，Cl）的反应也得到了NiR（Y）Ln类型的配合物，并形成了不对称的酮RCOR′。1与醇的反应导致醇的脱氢，得到了醛或酮。NiR（Y）Ln类型的配合物通过元素分析和光谱学（IR，NMR，可见光）进行了表征。trans-NiMe（OCOPh）（PEt\({}_{3}\)）\({}_{2}\)，NiMe（苯乙酮肟基）（PEt\({}_{3}\)）（11），NiMe（苯甲酰丙酮基）（PEt\({}_{3}\)）的NMR光谱显示了温度依赖性，表明在这些配合物中在NMR时间尺度上发生了快速动态反应。根据IR和NMR光谱学，11中的苯乙酮肟基配体被提议作为氧，氮-π-烯丙基配体。NiEt（OCOC\({}_{2}\)H\({}_{5}\)）（bpy）（8），NiEt（OCOC\({}_{6}\)H\({}_{5}\)）（bpy），和NiEt（Cl）（bpy）（14）发生歧化反应，得到了NiEt\({}_{2}\)（bpy）和NiY\({}_{2}\)（bpy）类型的配合物。二乙基酮也在8的歧化过程中产生。14与具有吸电子取代基的烯烃反应，得到了NiCl\({}_{2}\)（bpy）和Ni（烯烃）\({}_{2}\)（bpy）。

  DOI：

  10.1246/bcsj.54.2010

文献信息

• Preparation of Nickel Complexes with η²-Coordinated Fluorinated Ketones from Dialkylnickel Complexes
  作者：Yong-Joo Kim、Kohtaro Osakada、Akio Yamamoto

  DOI：10.1246/bcsj.62.964

  日期：1989.3

  Reactions of hexafluoroacetone and 2,2,2-trifluoroacetophenone with dialkylnickel complexes cause extrusion of the alkyl ligands to give nickel complexes having an η2-coordinated ketone and an auxiliary ligand such as bpy (2,2′-bipyridine) or dpe (1,2-bis(diphenylphosphino)ethane).

  六氟丙酮和2,2,2-三氟苯乙酮与二烷基镍络合物的反应会导致烷基配体的挤出，从而生成含有一个η2配位的酮和辅助配体如bpy（2,2'-联吡啶）或dpe（1,2-双(二苯基膦)乙烷）的镍络合物。
• Role of Electron-Deficient Olefin Ligands in a Ni-Catalyzed Aziridine Cross-Coupling To Generate Quaternary Carbons
  作者：Jesús G. Estrada、Wendy L. Williams、Stephen I. Ting、Abigail G. Doyle

  DOI：10.1021/jacs.0c02237

  日期：2020.5.13

  represents a promising ligand in this regard, the basis for its superior performance is not well understood. Here we describe a detailed mechanistic study of the aziridine cross-coupling reaction and the role of EDO ligands in facilitating Csp3-Csp3 bond formation. This analysis reveals that cross-coupling proceeds by a Ni0/II cycle with a NiII azametallacyclobutane catalyst resting state. Turnover-limiting

  我们之前报道了缺电子烯烃 (EDO) 配体 Fro-DO 的开发，该配体通过 Ni 催化的 Csp3-Csp3 与氮丙啶交叉偶联促进季碳中心的生成。相比之下，电子和结构相似的 EDO 配体如富马酸二甲酯和缺电子苯乙烯主要提供 β-氢化物消除副反应。只有少数催化剂系统已被确定通过 Ni 催化的 Csp3-Csp3 交叉偶联促进季碳的形成。尽管 Fro-DO 在这方面代表了一种很有前途的配体，但其卓越性能的基础尚不清楚。在这里，我们描述了氮丙啶交叉偶联反应的详细机理研究以及 EDO 配体在促进 Csp3-Csp3 键形成中的作用。该分析表明，交叉偶联通过 NiO/II 循环与 NiII 氮杂金属环丁烷催化剂静止状态进行。转换限制性 CC 还原消除发生在光谱可观察的 NiII-二烷基中间体与 EDO 结合。计算分析表明，Fro-DO 通过降低 LUMO 加速周转限制还原消除。然而，它在减少 Csp3-Csp3
• Reactions of Dialkylnickel(II) Complexes NiR₂L₂with Alkyl (or Aryl) Halides, R′COY (Y=Cl, Br, OPh, OCOPh), and CS₂
  作者：Takakazu Yamamoto、Teiji Kohara、Kohtaro Osakada、Akio Yamamoto

  DOI：10.1246/bcsj.56.2147

  日期：1983.7

  Reactions of Ni(CH3)2(bpy) (1), Ni(C2H5)2(bpy) (2) (bpy=2,2′-bipyridine), trans-Ni(CH3)2(triethylphosphine)2 (3), Ni(CH3)2(1,2-bis(diphenylphosphino)ethane) (4), and Ni(CH3)2(1,3-bis(diphenylphosphino)propane) (5) with alkyl or aryl halides, R′COY (Y=Cl, Br, OC6H5, OCOC6H5), and CS2 have been investigated. The reactions of NiR2L2 with alkyl or aryl halides are classified into three types of reactions

  Ni(CH3)2(bpy) (1)、Ni(C2H5)2(bpy) (2) (bpy=2,2'-联吡啶)、反式-Ni( )2(三乙基膦)2 (3) 的反应, Ni( )2(1,2-bis(diphenylphosphino)ethane) (4), and Ni( )2(1,3-bis(diphenylphosphino)propane) (5) 与烷基或芳基卤化物，R'COY (Y=Cl、Br、OC6H5、OCOC6H5) 和 CS2 已被研究。NiR2L2与烷基或芳基卤化物的反应按反应产物分为三种反应类型：A型：NiR2L2+R'X→NiX(R')L2+R–R，B型：NiR2L2+R'X→烷烃 (RH)+ 烯烃 (R'(-H)) 和 C 型：NiR2L2+R'X→NiR(X)L2+R-R'。配合物 1 和 2 主要进行 A 型反应。配合物 3 用 C6H5Br 处理得到 A 型反应产物，但用
• 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.
• Preparation and Properties of Monoalkylnickel(II) Complexes NiR(NR¹R²)L₂Having Imido, Imidazolato, or Methyl Phenylcarbamato-<i>N</i>Ligand
  作者：Takakazu Yamamoto、Teiji Kohara、Akio Yamamoto

  DOI：10.1246/bcsj.54.1720

  日期：1981.6

  Reactions of dialkylnickel(II) complexes NiR2L2 1 (R=CH3, C2H5; L=1/2 bpy(2,2′-bipyridine), 1/2 dpe (1,2-bis(diphenylphosphino)ethane), PEt3) with compounds having acidic N–H bonds (succinimide, phthalimide, diacetamide, pyromellitimide (1,2 : 4,5-benzenebis(dicarboximide)), imidazole) gave corresponding monoalkylnickel(II) complexes having Ni–N bond formulated as NiR(NR1R2)L2. A reaction of NiMe2(PEt3)2

  二烷基镍 (II) 与 NiR2L2 1 (R=CH3, C2H5; L=1/2 bpy(2,2'-联吡啶), 1/2 dpe (1,2-双(二苯基膦)乙烷), PEt3) 配合物的反应具有酸性 N-H 键的化合物（琥珀酰亚胺、邻苯二甲酰亚胺、二乙酰胺、均苯四甲酰亚胺（1,2 : 4,5-苯双（二甲酰亚胺））、咪唑）得到相应的具有 Ni-N 键的单烷基镍 (II) 配合物，公式为 NiR(NR1R2) L2。NiMe2(PEt3)2 与 OH 和异氰酸苯酯的反应得到 NiMe(N(Ph)COOMe)(PEt3)2。配合物的 IR、NMR 和可见光谱研究表明，Ni 的电负性通过用 NR1R2 配体替换 1 中的两个 R 基团之一而增强。NiMe(NR1R2)(PEt3)2 型配合物的 NMR 谱表明它们具有反式构型。单烷基镍 (II) 配合物的热解开始温度比 1 高 80–100 °C，释放出